TW201338970A - Copper-clad laminated plate having primer layer, and wiring board using the laminated plate - Google Patents

Copper-clad laminated plate having primer layer, and wiring board using the laminated plate Download PDF

Info

Publication number
TW201338970A
TW201338970A TW101111334A TW101111334A TW201338970A TW 201338970 A TW201338970 A TW 201338970A TW 101111334 A TW101111334 A TW 101111334A TW 101111334 A TW101111334 A TW 101111334A TW 201338970 A TW201338970 A TW 201338970A
Authority
TW
Taiwan
Prior art keywords
layer
copper
resin
group
clad laminate
Prior art date
Application number
TW101111334A
Other languages
Chinese (zh)
Inventor
Tomoki Okano
Ryutaro Tanaka
Makoto Uchida
Makoto Tsuji
Shigeo Hayashimoto
Kenji Sekine
Original Assignee
Nippon Kayaku Kk
Jx Nippon Mining & Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Kk, Jx Nippon Mining & Metals Corp filed Critical Nippon Kayaku Kk
Priority to TW101111334A priority Critical patent/TW201338970A/en
Publication of TW201338970A publication Critical patent/TW201338970A/en

Links

Landscapes

  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

To provide a copper-clad laminated plate which has a primer resin (B) layer comprising solvent-soluble polyimide, on the surface of a coated layer formed on the copper foil (A) which is not subjected to roughing treatment, and a polyimide layer (D) directly adherung on the primer resin (B) layer, and satisfies the following requirements: (1) the coated layer is constituted of a Ni layer and a Cr layer sequentially laminated from the surface of the copper foil, (2) the coating amounts of Ni and Cr in the coated layer are 15 to 440 &mgr; g/dm<SP>2</SP> and 15 to 210 &mgr; g/dm<SP>2</SP>, respectively, (3) the maximum value of the thickness of the coated layer is 0.5 to 5 nm, and the minimum value is not smaller than 80% of the maximum value, (4) the solvent-soluble polyimide is a closed cyclic polyimide obtained by reacting (i) oxydiphthalic dianhydride or (ii) the oxydiphthalic dianhydride and at least one aromatic tetrabasic acid dianhydride other than the oxydiphthalic dianhydride, with (iii) bis(aminophenoxy)benzene or (iv) the bis(aminophenoxy)benzene and at least one aromatic diamine other than the bis(aminophenoxy)benzene, and the number average molecular weight of this polyimide is 1, 000 to 50, 000, and the weight average molecular weight is 5, 000 to 500, 000. This invention provides a copper-clad laminated plate having high adhesion (high peel strength) between the copper foil not roughened and the primer resin layer (B), and maintaining high adhesion even at high temperature and high moisture, and excellent in solder-heat resistance, furthermore, having an anti-rust effect to metal foil at imidization, and preferably, not causing foaming when imidizing a polyamic acid, and reducing curl even after etching.

Description

具有底覆層之覆銅積層板及使用該積層板之配線基板 Copper-clad laminate having undercoat layer and wiring substrate using the same

本發明係關於一種覆銅積層板，係在無粗糙化之銅箔基材表面上，具有由Ni層及Cr層而組成之被覆層、在該被覆層上之聚醯亞胺樹脂之底覆層、以及在該底覆層上之絕緣用等之聚醯亞胺層，且使用於可撓性印刷配線板等。 The present invention relates to a copper clad laminate which has a coating layer composed of a Ni layer and a Cr layer on the surface of a non-roughened copper foil substrate, and a primer layer of a polyimide resin on the coating layer. The layer and the polyimide layer for insulation such as the undercoat layer are used for a flexible printed wiring board or the like.

聚醯亞胺樹脂薄膜之一般用途係列舉：貼合以銅箔為代表之金屬箔的單面或雙面可撓性積層板、可撓性印刷配線板用覆蓋層以及多層基板用層間絕緣薄膜等。其中，聚醯亞胺樹脂和金屬箔並未隔著接著劑層而直接地貼合者稱為2層CCL，該2層CCL的積層板雖有配線之細微化或基板之耐熱性方面的優點，但卻有聚醯亞胺樹脂和金屬箔之密著性不足之問題。2層CCL之製造方法，現在主流係藉由加熱而對於塗佈在金屬箔上之聚醯亞胺樹脂前驅物進行醯亞胺化。此外已知透過作為接著層之熱塑性聚醯亞胺而加熱壓合聚醯亞胺薄膜和金屬箔之層合法、或者是在聚醯亞胺薄膜表面設置之濺鍍層上鍍覆金屬箔之濺鍍法等。 A general-purpose series of a polyimide film is a single-sided or double-sided flexible laminate laminated with a metal foil represented by a copper foil, a cover layer for a flexible printed wiring board, and an interlayer insulating film for a multilayer substrate. Wait. Among them, the polyimide film and the metal foil are not directly bonded to each other via the adhesive layer, and are called a two-layer CCL. The two-layer CCL laminated board has the advantages of fine wiring or heat resistance of the substrate. However, there is a problem that the adhesion of the polyimide resin and the metal foil is insufficient. In the production method of the two-layer CCL, the mainstream is currently subjected to ruthenium imidization of the polyimide film precursor coated on the metal foil by heating. Furthermore, it is known to heat-press a laminate of a polyimide film and a metal foil through a thermoplastic polyimide which is an adhesive layer, or to deposit a metal foil on a sputtering layer provided on the surface of a polyimide film. Law and so on.

向來在該等印刷配線板之製造中，可使用在銅箔單面上附著細微銅粒子等並藉由粗糙化處理而在表面形成凹凸之銅箔。在使用粗糙化處理銅箔時，藉由在銅箔表面之凹凸形狀埋入樹脂而得到固定效果，因此可以改善銅箔和聚醯亞胺樹脂之密著性。 In the production of such a printed wiring board, a copper foil having fine copper particles or the like adhered to one surface of the copper foil and having irregularities formed on the surface by roughening treatment can be used. When the roughened copper foil is used, the fixing effect is obtained by embedding the resin in the uneven shape on the surface of the copper foil, so that the adhesion between the copper foil and the polyimide resin can be improved.

但是，在粗糙化處理銅箔之表面，通常塗佈作為防銹 劑等之胺化合物、長鏈烷基化合物或聚矽氧系化合物等而作為表面處理劑，因此在未由銅箔表面除去該等而藉由鑄模法塗佈聚醯亞胺樹脂前驅物時，所得到之2層CCL銅箔和聚醯亞胺樹脂層之剝離強度會降低。該等表面處理劑可藉由經過脫脂步驟或軟蝕刻(soft-ethcing)等之煩雜步驟而除去，但是，除去表面處理劑之銅箔表面係曝露於大氣或聚醯亞胺樹脂前驅物下，而有容易腐蝕氧化之問題。 However, on the surface of roughened copper foil, it is usually coated as rustproof As a surface treatment agent, an amine compound such as a reagent, a long-chain alkyl compound, or a polyoxyalkylene compound is used as a surface treatment agent, and thus the polyimide precursor resin precursor is coated by a mold method without removing the surface of the copper foil. The peel strength of the obtained two-layer CCL copper foil and polyimine resin layer was lowered. The surface treatment agent may be removed by a troublesome step such as a degreasing step or soft-ethcing, but the surface of the copper foil from which the surface treatment agent is removed is exposed to the atmosphere or the polyimide precursor of the polyimide. There is a problem of easy corrosion and oxidation.

在專利文獻1，揭示以提高銅箔和基材樹脂之非熱塑性聚醯亞胺薄膜之密著性為目的，而在非熱塑性聚醯亞胺薄膜之表面上塗佈熱塑性聚醯亞胺之清漆，在形成熱塑性聚醯亞胺層之後與銅箔熱壓合之層合法。但是，無法得到常溫時之剝離強度、曝露於高溫條件後之剝離強度以及曝露於濕熱條件後之剝離強度三者皆滿足者。此外，使用該清漆之層合法係有尺寸安定性變差之傾向。此外，在非熱塑性聚醯亞胺薄膜之氣體穿透性低時，聚醯亞胺薄膜和該清漆之界面容易產生由殘留溶劑或分解物引起之起泡，因此必須在基材使用高度氣體穿透性之聚醯亞胺薄膜。 Patent Document 1 discloses that a varnish of a thermoplastic polyimide pigment is coated on the surface of a non-thermoplastic polyimide film for the purpose of improving the adhesion of a non-thermoplastic polyimide film of a copper foil and a base resin. A layer that is thermocompression bonded to a copper foil after forming a layer of thermoplastic polyimide. However, it is not possible to obtain the peel strength at normal temperature, the peel strength after exposure to high temperature conditions, and the peel strength after exposure to moist heat conditions. Further, the use of the lacquer layer has a tendency to deteriorate dimensional stability. In addition, when the gas permeability of the non-thermoplastic polyimide film is low, the interface between the polyimide film and the varnish is likely to cause foaming caused by residual solvent or decomposition product, and therefore it is necessary to wear a high gas in the substrate. A permeable polyimide film.

此外，在專利文獻2，揭示為了提高對於聚醯亞胺系樹脂之密著性，因此在粗糙化處理或非粗糙化處理之銅箔表面設置Ni層及/或Cr層之方法。具體來說係揭示在銅箔表面形成藉由Ni電鍍之Ni層及/或藉由電鍍法或鉻酸鹽處理而形成之Cr層，並在其上面塗佈聚醯胺酸清漆，在乾燥後進行醯亞胺化而成為形成聚醯亞胺層之覆銅積層板。該方法認定會提升一定程度之密著性，但是並未發現特異之 密著力，而且滿足耐熱剝離強度及耐濕熱後剝離強度兩者。 Further, Patent Document 2 discloses a method of providing a Ni layer and/or a Cr layer on the surface of a roughened or non-roughened copper foil in order to improve the adhesion to the polyimide resin. Specifically, it is disclosed that a Ni layer formed by Ni plating and/or a Cr layer formed by electroplating or chromate treatment is formed on the surface of the copper foil, and a polyamic acid varnish is coated thereon, after drying The yttrium imidization is carried out to form a copper-clad laminate which forms a polyimide layer. This method is believed to increase a certain degree of closeness, but no specificity has been found. It has a close contact and meets both heat-resistant peel strength and wet heat-resistant peel strength.

此外，在專利文獻3，揭示以提高無粗糙化處理銅箔和聚醯亞胺樹脂(絕緣樹脂層)間之接著性為目的，而包含環氧樹脂和特定閉環型聚醯亞胺之底覆層用樹脂組成物。 Further, Patent Document 3 discloses a primer comprising an epoxy resin and a specific closed-loop polyimine for the purpose of improving the adhesion between the roughened copper foil and the polyimide resin (insulating resin layer). The resin composition for the layer.

[先前技術文獻] [Previous Technical Literature] (專利文獻) (Patent Literature)

專利文獻1：日本特開2000-52483號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-52483

專利文獻2：日本特開2006-222185號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-222185

專利文獻3：日本特開2010-31167號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2010-31167

如果可將無施行粗糙化處理之銅箔使用於印刷配線板之製造的話，則可省略銅箔之粗糙化處理步驟，能夠大幅度地減低生產成本。此外，因在電路蝕刻中不需要設置用以溶解粗糙化處理部分之過蝕刻(over-etching)時間，所以也可削減總蝕刻成本。 If the copper foil which is not subjected to the roughening treatment can be used for the production of a printed wiring board, the roughening treatment step of the copper foil can be omitted, and the production cost can be greatly reduced. Further, since it is not necessary to provide an over-etching time for dissolving the roughened portion in the circuit etching, the total etching cost can also be reduced.

而且，除了可藉由消除粗糙化部分之厚度而進行印刷配線板之薄型化以外，因在凹凸部分蝕刻之樹脂並無殘留作為蝕刻殘渣，因此可形成更細微之配線圖案。此外，因配線表面之電阻減少，特別在使用高頻電流時，因表皮效果而提高銅箔表面之電流密度，因此能夠提高印刷配線板之特性。 Further, in addition to thinning the printed wiring board by eliminating the thickness of the roughened portion, the resin etched in the uneven portion does not remain as an etching residue, so that a finer wiring pattern can be formed. Further, since the electric resistance of the wiring surface is reduced, particularly when a high-frequency current is used, the current density of the surface of the copper foil is increased by the skin effect, so that the characteristics of the printed wiring board can be improved.

本發明之目的係提供一種覆銅積層板，其係未對於銅箔進行粗糙化處理且以鑄模法而得之可撓性印刷配線板用 覆銅積層板，其中，銅箔和基材樹脂之聚醯亞胺樹脂具有良好之接著性，同時具有銅箔之防銹效果。此外，本發明之目的係提供一種覆銅積層板，在較佳之形態中，該覆銅積層板並無製造該覆銅積層板時之殘留溶劑等所造成之起泡，並減低蝕刻後之捲曲之發生。 An object of the present invention is to provide a copper clad laminate which is used for a flexible printed wiring board which is not subjected to roughening treatment of a copper foil and which is obtained by a molding method. A copper clad laminate in which the copper foil and the base resin of the base resin have good adhesion and have a rust preventing effect of the copper foil. Further, an object of the present invention is to provide a copper clad laminate which, in a preferred embodiment, does not have foaming caused by residual solvent or the like when the copper clad laminate is manufactured, and reduces curl after etching. It happened.

本發明者們係為了解決前述之課題而全心進行研究，結果發現藉由在銅箔上形成極為薄且厚度均勻之Ni層及Cr層(被覆層)，並使用特定構造之聚醯亞胺樹脂作為底覆層樹脂，而可解決前述課題，從而完成本發明。 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a polyimide layer having a specific structure is formed by forming an extremely thin and uniform thickness of a Ni layer and a Cr layer (coating layer) on a copper foil. The resin can be used as a primer resin to solve the aforementioned problems, and the present invention has been completed.

也就是說，本發明係關於下列1至9所述之發明。 That is, the present invention relates to the inventions described in the following 1 to 9.

1.一種覆銅積層板，其係在無施行粗糙化處理之銅箔(A)上設置之被覆層表面上，具有由溶媒可溶性聚醯亞胺組成之底覆層樹脂(B)層，並且在其上具有直接接著之聚醯亞胺層(D)，而且滿足下列(1)至(4)要件之覆銅積層板，(1)該被覆層係藉由自銅箔表面依序積層之Ni層及Cr層而構成、(2)該被覆層之Ni及Cr被覆量分別為15至440μg/dm2及15至210μg/dm2、(3)該被覆層之厚度最大值係0.5至5nm，且最小值為最大值之80%以上、(4)溶媒可溶性聚醯亞胺係藉由下列(i)或(ii)所述之芳香族四元酸二酐和下列之(iii)或(iv)所述之芳香族二胺之間之反應而得到之數平均分子量為1,000至50,000且重量 平均分子量為5,000至500,000之閉環型聚醯亞胺樹脂；(i)下式(1)所表示之氧基二苯二甲酸二酐 (ii)該氧基二苯二甲酸二酐、和其他芳香族四元酸二酐之至少1種的兩種者；(iii)下式(2)所表示之雙(胺基苯氧基)苯 (iv)該雙(胺基苯氧基)苯、和其他芳香族二胺之至少1種的兩種者。 A copper clad laminate having a bottom coat resin (B) layer composed of a solvent-soluble polyimine on a surface of a coating layer provided on a copper foil (A) which is not subjected to roughening treatment, and a copper-clad laminate having a layer of polyimine directly adjacent thereto (D) and satisfying the following requirements (1) to (4), (1) the coating layer is sequentially laminated from the surface of the copper foil The Ni layer and the Cr layer are formed, (2) the Ni and Cr coating amounts of the coating layer are 15 to 440 μg/dm 2 and 15 to 210 μg/dm 2 , respectively, and (3) the maximum thickness of the coating layer is 0.5 to 5 nm. And the minimum value is 80% or more of the maximum value, and (4) the solvent-soluble polyimine is the aromatic tetrabasic dianhydride described in the following (i) or (ii) and the following (iii) or Iv) a closed-loop polyimine resin having a number average molecular weight of 1,000 to 50,000 and a weight average molecular weight of 5,000 to 500,000 obtained by the reaction between the aromatic diamines; (i) represented by the following formula (1) Oxydiphthalic dianhydride (ii) at least one of the oxydiphthalic dianhydride and the other aromatic tetrabasic acid dianhydride; (iii) the bis(aminophenoxy group) represented by the following formula (2) benzene (iv) at least one of the bis(aminophenoxy)benzene and the other aromatic diamine.

2.前述1所述之覆銅積層板，其中，式(2)以外之芳香族二胺之至少1種係由3,3’-二胺基-4,4’-二羥基二苯基醚、3,3’-二胺基-4,4’-二羥基二苯基碸、3,3’-二胺基-4,4’-二羥基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、2,2-雙(3-胺基-4-羥基苯基)丙烷、1,3-六氟-2,2-雙(3-胺基-4-羥基苯基)丙烷、1,3-雙(4-胺基-3-羥基苯氧基)苯和9,9’-雙(3-胺基-4-羥基苯基)芴所組成群組選出至少1種之二胺基二酚(diaminodiphenol)類。 2. The copper clad laminate according to the above 1, wherein at least one of the aromatic diamines other than the formula (2) is 3,3'-diamino-4,4'-dihydroxydiphenyl ether. , 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4 , 4'-diaminobiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyl Selective group consisting of phenyl)propane, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, and 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene One type of diaminodiphenol.

3.前述1所述之覆銅積層板，其中，使用於前述反應之四元酸二酐為(i)或(ii)或(iii)，(i)式(1)之氧基二苯二甲酸二酐單獨； (ii)式(1)之氧基二苯二甲酸二酐，和由下式(3)所示之聯苯基四羧酸二酐及均苯四甲酸酐所組成群組選出至少1種之芳香族四元酸二酐兩種併用者； (iii)在前述(i)或(ii)中復加入其他之芳香族四元酸二酐之至少1種之兩種或三種併用者；使用於前述反應之二胺係(i)或(ii)，(i)式(2)之雙(胺基苯氧基)苯，和由下式(4)所述之芳香族二胺所組成群組選出至少1種之兩種併用者 (式(4)中，R4係表示甲基，R5係表示氫原子、甲基、乙基、甲氧基或三氟甲基)； (ii)在前述(i)中復加入前述(i)以外之芳香族二胺之至少1種之三種併用者。 3. The copper clad laminate according to the above 1, wherein the tetrabasic acid dianhydride used in the above reaction is (i) or (ii) or (iii), (i) the oxydiphenyl compound of the formula (1). Formic acid dianhydride alone; (ii) an oxydiphthalic dianhydride of the formula (1), and a group consisting of biphenyltetracarboxylic dianhydride and pyromellitic anhydride represented by the following formula (3) Selecting at least one type of aromatic tetrabasic acid dianhydride to be used together; (iii) a combination of two or more of at least one of the other aromatic tetrabasic dianhydrides added to the above (i) or (ii); the diamine system (i) or (ii) used in the aforementioned reaction And (i) bis(aminophenoxy)benzene of the formula (2), and at least one selected from the group consisting of the aromatic diamines of the following formula (4) (In the formula (4), R 4 represents a methyl group, R 5 represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group or a trifluoromethyl group); (ii) the above-mentioned (i) is added to the above ( i) Any combination of at least one of the aromatic diamines other than i).

4.前述1至3中任一項所述之覆銅積層板，其中，在無施行粗糙化處理之銅箔(A)上設置之被覆層係藉由濺鍍法而形成。 4. The copper clad laminate according to any one of the above 1 to 3, wherein the coating layer provided on the copper foil (A) which is not subjected to the roughening treatment is formed by a sputtering method.

5.前述1至4中任一項所述之覆銅積層板，其中，直接接著於底覆層樹脂(B)層之聚醯亞胺層(D)，係將包含對應之聚醯胺酸之聚醯亞胺樹脂前驅物(C)層加熱進行醯亞胺化而得之聚醯亞胺層(D)。 The copper-clad laminate according to any one of the above 1 to 4, wherein the polyimine layer (D) directly following the undercoat resin (B) layer contains the corresponding poly-proline The polyimine resin precursor (C) layer is heated to carry out the quinone imidization of the polyimine layer (D).

6.前述1至5中任一項所述之覆銅積層板，其中，底覆層樹脂(B)層係將包含底覆層樹脂(B)之樹脂清漆塗佈在設置於銅箔(A)上之被覆層表面並乾燥而得者，且該底覆層樹脂(B)層之厚度係0.5至20μm。 The copper clad laminate according to any one of the above 1 to 5, wherein the undercoat resin (B) layer is coated with a resin varnish containing the undercoat resin (B) on the copper foil (A). The surface of the coating layer is dried and dried, and the thickness of the undercoat resin (B) layer is 0.5 to 20 μm.

7.前述6所述之覆銅積層板，其中，包含底覆層樹脂(B)之樹脂清漆係將溶媒可溶性聚醯亞胺溶解於由N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基甲醯胺、γ-丁內酯、環戊酮及安息香酸甲酯所組成群組選出至少1種之溶媒之樹脂清漆。 7. The copper clad laminate according to the above 6, wherein the resin varnish comprising the undercoat resin (B) dissolves the solvent-soluble polyimine in N-methyl-2-pyrrolidone, N, N-di Selecting at least one solvent from the group consisting of methyl acetamide, N,N-dimethylformamide, N-methylformamide, γ-butyrolactone, cyclopentanone, and methyl benzoate Resin varnish.

8.前述5至7中任一項所述之覆銅積層板，其中，包含聚醯胺酸之聚醯亞胺樹脂前驅物(C)層係含有下式(7)所示之末端具有胺基之聚醯胺酸、以及下式(8)所示之四羧酸衍生物， (式(7)中，R6係表示4價之芳香族基，R7係表示2價之芳香族基，x係平均重複數而表示1以上之實數) (式(8)中，R8係表示4價之芳香族基，R9係表示氫原子或C1至C3烷基。) The copper-clad laminate according to any one of the above-mentioned items 5 to 7, wherein the poly(imide) resin precursor (C) layer containing polyphthalic acid contains an amine having a terminal represented by the following formula (7) a polyamic acid, and a tetracarboxylic acid derivative represented by the following formula (8), (In the formula (7), R 6 represents a tetravalent aromatic group, R 7 represents a divalent aromatic group, and x is an average repeat number and represents a real number of 1 or more) (In the formula (8), R 8 represents a tetravalent aromatic group, and R 9 represents a hydrogen atom or a C1 to C3 alkyl group.)

9.一種配線基板，其係使用前述1至8中任一項所述之覆銅積層板。 A wiring board using the copper clad laminate according to any one of the above 1 to 8.

本發明之覆銅積層板的特徵係無粗糙化銅箔和聚醯亞胺層(D)具有高度密著性(剝離強度)，且放置在過度嚴酷之高溫、高濕度條件下後也維持高度密著性，同時焊接耐熱性也良好。藉由薄化且厚度均勻地形成Ni層及Cr層，並且使用由包含特定成份之聚醯亞胺所組成之底覆層樹脂(B)層而達成該效果。認為該效果係藉由構成被覆層之Ni層及Cr層之金屬原子之排列週期、以及底覆層樹脂(B)具有之柔軟之醚鍵係適合於醯亞胺基之適當重複長度，且底覆層 樹脂(B)層在被覆層顯示高度密著性，而得該效果。 The copper clad laminate of the present invention is characterized in that the roughened copper foil and the polyimide layer (D) have high adhesion (peel strength) and are maintained at an excessively high temperature and high humidity. Adhesion and solder heat resistance are also good. This effect is achieved by thinning and uniformly forming a Ni layer and a Cr layer, and using a bottom coating resin (B) layer composed of a polyimine containing a specific component. It is considered that the effect is that the arrangement period of the metal atoms constituting the Ni layer and the Cr layer of the coating layer and the soft ether bond of the undercoat resin (B) are suitable for the appropriate repeat length of the quinone imine group, and the bottom Coating The resin (B) layer exhibits high adhesion on the coating layer, and this effect is obtained.

此外，本發明之覆銅積層板係藉由具有前述底覆層樹脂(B)層，而也具有作為銅箔(A)之防銹處理層之效果。 Further, the copper clad laminate of the present invention has the effect of being a rust-preventing layer of the copper foil (A) by having the undercoat resin (B) layer.

此外，本發明之覆銅積層板，在塗佈包含聚醯胺酸之聚醯亞胺樹脂前驅物(C)清漆並醯亞胺化所得之層(聚醯亞胺樹脂前驅物(C)層)而形成聚醯亞胺層(D)時，起因於殘留溶劑及樹脂骨架之分解反應之起泡變少，在理想之形態中，其特徵為藉由併用特定芳香族胺而不會產生起泡。特別是併用式(2)之二胺成份和二羥基二胺基聯苯而作為底覆層樹脂(B)之聚醯亞胺之二胺成份時，該效果更大。 Further, the copper clad laminate of the present invention is obtained by coating a layer of a polyamidene resin precursor (C) varnish containing poly-proline, and imidizing the layer (polyimine resin precursor (C) layer). When the polyimine layer (D) is formed, the foaming due to the decomposition reaction of the residual solvent and the resin skeleton is small, and in a preferred embodiment, it is characterized in that a specific aromatic amine is used in combination and does not occur. bubble. In particular, when the diamine component of the formula (2) and the dihydroxydiamine biphenyl are used in combination as the diamine component of the polyamidene of the undercoat resin (B), the effect is greater.

此外，以往以賦予密著性為目的而在底覆層樹脂導入醚鍵時，底覆層樹脂之線膨脹係數增加，並在蝕刻最後得到之積層板之銅箔之際會有產生捲曲之問題。在本發明之理想形態中，底覆層樹脂(B)係除了醚鍵以外，還適度地包含高剛直性及堆積性之構造，因此不會隨著線膨脹係數增加而抑制蝕刻後之捲曲。因此，本發明之覆銅積層板係實用於電機電子材料領域而極為有用。 In addition, when the ether bond is introduced into the undercoat resin for the purpose of imparting adhesion, the linear expansion coefficient of the undercoat resin is increased, and the problem of curling occurs when the copper foil of the laminate obtained at the end of etching is formed. In a preferred embodiment of the present invention, the undercoat resin (B) has a structure including high rigidity and deposition property in addition to the ether bond, and therefore does not suppress the curl after etching as the coefficient of linear expansion increases. Therefore, the copper clad laminate of the present invention is extremely useful in the field of motor electronic materials.

本發明中，設置有被覆層且無施行粗糙化處理之銅箔(A)(以下僅稱為「銅箔A」)只要是表面粗糙度(Rz)為2μm以下的話，則可以使用壓延銅箔及電解銅箔任一種。通常由彎曲強度等之方面來看的話則較佳是壓延銅箔。該銅箔其表面(表面粗糙度Rz=2μm以下)披覆之被覆層係由銅箔基材起依序以Ni層、Cr層之順序而構成。被覆層之被 覆量係Ni通常為15至440μg/dm2之範圍，Cr通常為15至210μg/dm2之範圍。 In the present invention, the copper foil (A) (hereinafter simply referred to as "copper foil A") provided with the coating layer and not subjected to the roughening treatment may be a rolled copper foil as long as the surface roughness (Rz) is 2 μm or less. And any one of electrolytic copper foil. The rolled copper foil is preferably used in view of the bending strength and the like. The coating layer on which the surface of the copper foil (surface roughness Rz = 2 μm or less) is coated in the order of the Ni layer and the Cr layer in this order from the copper foil substrate. The coating amount of the coating layer of Ni-based is generally from 15 to 440μg / dm 2 of the range, Cr is generally in the range of 15 to 210μg / dm 2 of.

此外，被覆層之厚度最大值通常為0.5至5nm之範圍，且最小值通常為最大值之80%以上。 Further, the maximum thickness of the coating layer is usually in the range of 0.5 to 5 nm, and the minimum value is usually 80% or more of the maximum value.

若大幅損害被覆量、被覆層厚度及被覆層之厚度均勻性(厚度最小值係最大值之80%以上)，則會降低和聚醯亞胺(B)層之密著性、蝕刻性、柔軟性、銅箔之抗氧化效果等之特性。在本發明中，要得到本發明之特性，被覆層之厚度均勻性係特別重要。 If the coating amount, the thickness of the coating layer, and the thickness uniformity of the coating layer (80% or more of the maximum thickness) are greatly impaired, the adhesion to the polyimide layer (B) layer, etching property, and softness are lowered. Properties, anti-oxidation effects of copper foil, etc. In the present invention, in order to obtain the characteristics of the present invention, the thickness uniformity of the coating layer is particularly important.

此外，根據目的不同，Ni被覆量係15至未滿300μg/dm2、較佳為20至200μg/dm2左右、更佳為40至180μg/dm2左右。 Further, depending on the purpose, Ni-based coating amount of 15 to less than 300μg / dm 2, preferably 20 to 200μg / dm 2 or so, more preferably from 40 to 180μg / dm 2 or so.

Cr被覆量係15至未滿180μg/dm2、較佳為20至150μg/dm2左右、更佳為30至100μg/dm2左右。 The Cr coating amount is 15 to less than 180 μg/dm 2 , preferably about 20 to 150 μg/dm 2 , more preferably about 30 to 100 μg/dm 2 .

若Ni被覆量及Cr被覆量分別為前述之範圍則無限定。通常，在Ni被覆量為1質量份時，Cr被覆量係多於0.5質量份，較佳為1質量份以下之比例，更佳為0.6至1質量份之比例。 The Ni coating amount and the Cr coating amount are not limited as long as they are within the above ranges. In general, when the Ni coating amount is 1 part by mass, the Cr coating amount is more than 0.5 parts by mass, preferably 1 part by mass or less, more preferably 0.6 to 1 part by mass.

被覆層之厚度(Ni層及Cr層之合計厚度)之最大值係由於目的不同而為0.5至4nm左右，更佳為1至4nm左右。依情形而定最佳為1.5至4nm左右。 The maximum value of the thickness of the coating layer (the total thickness of the Ni layer and the Cr layer) is about 0.5 to 4 nm, more preferably about 1 to 4 nm, depending on the purpose. The optimum is about 1.5 to 4 nm depending on the situation.

此外，被覆層之厚度係可使用穿透型電子顯微鏡而以目視觀察被覆層之剖面，並藉此測定。由Ni層及Cr層組成之被覆層較佳為藉由濺鍍法而形成。在藉由濺鍍法形成 Ni層及Cr層時通常使用濺鍍裝置。濺鍍裝置如可形成前述被覆層的話，則可以是市面販賣之任一種。以具體揭示於專利文獻3之藉由電鍍法而形成Ni層、且藉由電鍍法或鉻酸鹽處理而形成Cr層時，不容易形成均勻厚度(被覆層之厚度最小值係最大值之80%以上)之被覆層，無法得到和底覆層樹脂之特異密著性。 Further, the thickness of the coating layer can be measured by visually observing the cross section of the coating layer using a transmission electron microscope. The coating layer composed of the Ni layer and the Cr layer is preferably formed by sputtering. Formed by sputtering A sputtering device is usually used for the Ni layer and the Cr layer. If the sputtering apparatus can form the above-mentioned coating layer, it can be either commercially available. When a Cr layer is formed by a plating method specifically disclosed in Patent Document 3 and a Cr layer is formed by a plating method or a chromate treatment, it is not easy to form a uniform thickness (the minimum thickness of the coating layer is the maximum value of 80) The coating layer of % or more) cannot obtain the specific adhesion to the undercoat resin.

作為本發明之底覆層樹脂(B)使用之溶媒可溶性聚醯亞胺，係藉由至少包含前式(1)所示之氧基二苯二甲酸二酐之四元酸二酐、和至少包含前述式(2)所示之雙(胺基苯氧基)苯之二胺的加成反應而得到之聚醯胺酸，復進行脫水閉環而得溶媒可溶性聚醯亞胺。 The solvent-soluble polyimine used as the undercoat resin (B) of the present invention is a tetrabasic acid dianhydride containing at least the oxydiphthalic dianhydride represented by the above formula (1), and at least The polylysine obtained by the addition reaction of the bis(aminophenoxy)benzene diamine represented by the above formula (2) is subjected to dehydration ring closure to obtain a solvent-soluble polyimine.

具體表示前式(1)所表示之氧基二苯二甲酸二酐係可列舉下式(9)所述之化合物。該等化合物係可使用一種，也可使用複數種。通常係使用一種。 Specifically, the oxydiphthalic dianhydride represented by the above formula (1) is a compound represented by the following formula (9). These compounds may be used alone or in combination of plural kinds. Usually one is used.

此外，前式(2)所示之雙(胺基苯氧基)苯係可以列舉下式(10)所述之化合物。該等化合物係可使用一種，也可使用複數種。通常係使用一種。 Further, the bis(aminophenoxy)benzene represented by the above formula (2) may, for example, be a compound of the following formula (10). These compounds may be used alone or in combination of plural kinds. Usually one is used.

作為前述本發明之底覆層樹脂(B)使用之溶媒可溶性 聚醯亞胺係數平均分子量為1,000至50,000且重量平均分子量為5,000至500,000之溶媒可溶性閉環型聚醯亞胺。 Solvent solubility as the undercoat resin (B) of the present invention A solvent soluble closed-loop polyimine having a polyimine molecular weight average molecular weight of 1,000 to 50,000 and a weight average molecular weight of 5,000 to 500,000.

藉由前述之四元酸二酐和二胺之加成反應而合成聚醯胺酸，以及接著藉由脫水閉環而形成聚醯亞胺之一連串反應，較佳為於1鍋盆進行。 The polyamine acid is synthesized by the addition reaction of the above tetrabasic acid dianhydride and the diamine, and then a series of reactions of polyamidomine is formed by dehydration ring closure, preferably in a pot.

使用於加成反應之二胺之使用量係相對於使用之四元酸二酐所具有之酸酐基1當量，而使得二胺所具有之胺基通常成為0.5至2.0當量、較佳為0.8至1.2當量、更佳為0.9至1.1當量之量。 The diamine used in the addition reaction is used in an amount of 1 equivalent based on the acid anhydride group of the tetrabasic acid dianhydride used, so that the amine group of the diamine usually has 0.5 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents, more preferably from 0.9 to 1.1 equivalents.

藉由使四元酸二酐和二胺之使用比率為前述之範圍，而得到數平均分子量為1,000至50,000、更佳為5,000至50,000且重量平均分子量為5,000至500,000、更佳為10,000至300,000之聚醯亞胺。此外，在加成反應之際過剩地使用二胺時，使用之二胺鍵結於兩末端並得到具有末端胺基之聚醯亞胺，過剩地使用四元酸二酐時，使用之酸酐鍵結於兩末端並得到具有末端酸酐基之聚醯亞胺。使用相等莫耳數之二胺和四元酸二酐時，得到在末端隨機地具有胺基和酸酐基之聚醯亞胺。 By using the ratio of the use of the tetrabasic acid dianhydride and the diamine to the aforementioned range, the number average molecular weight is from 1,000 to 50,000, more preferably from 5,000 to 50,000, and the weight average molecular weight is from 5,000 to 500,000, more preferably from 10,000 to 300,000. Polyimine. Further, when the diamine is excessively used in the addition reaction, the diamine used is bonded to both ends to obtain a polyimine having a terminal amine group, and when the tetrabasic acid dianhydride is excessively used, the acid anhydride bond is used. The two ends are attached and a polyimine having a terminal acid anhydride group is obtained. When an equal molar number of diamine and tetrabasic acid dianhydride are used, a polyimine having an amine group and an acid anhydride group at the terminal is randomly obtained.

數平均分子量及重量平均分子量過小時，難以發現聚醯亞胺原本具有之耐熱性和機械強度，同時設置於銅箔(A)上之被覆層之表面容易受到底覆樹脂(B)中之末端胺基或末端酸酐基之影響。此外，數平均分子量及重量平均分子量過大時，作為溶解液時之黏度變高而難以形成底覆層之薄膜，同時降低被覆層和底覆層之接著性。 When the number average molecular weight and the weight average molecular weight are too small, it is difficult to find the heat resistance and mechanical strength originally possessed by the polyimide, and the surface of the coating layer provided on the copper foil (A) is easily exposed to the end of the undercoat resin (B). The effect of an amine group or a terminal acid anhydride group. Further, when the number average molecular weight and the weight average molecular weight are too large, the viscosity as a solution liquid becomes high, and it is difficult to form a film of the undercoat layer, and the adhesion between the coating layer and the undercoat layer is lowered.

此外，本發明之「溶媒可溶性聚醯亞胺」係溶解於有機溶劑時會得到至少5質量%以上濃度之溶解液之聚醯亞胺，較佳為10質量%以上。此外，數平均分子量及重量平均分子量係表示根據凝膠滲透色譜法之測定結果而以聚苯乙烯換算出之分子量。 Further, the "solvent-soluble polyimine" of the present invention is a polyimine which is obtained by dissolving in a concentration of at least 5% by mass or more, preferably 10% by mass or more, in an organic solvent. Further, the number average molecular weight and the weight average molecular weight are molecular weights in terms of polystyrene based on the measurement results by gel permeation chromatography.

本發明作為底覆樹脂(B)使用之溶媒可溶性聚醯亞胺係可作為四元酸二酐成份，可以單獨使用前述式(1)之氧基二苯二甲酸酐，也可以併用其他之芳香族四元酸二酐，此外，即使是作為二胺成份，也可單獨使用前述式(2)之雙(胺基苯氧基)苯，也可以併用其他之芳香族二胺。 The solvent-soluble polyimine which is used as the undercoat resin (B) of the present invention can be used as the tetrabasic dianhydride component, and the oxydiphthalic anhydride of the above formula (1) can be used singly or in combination with other aromatics. The tetrabasic acid dianhydride may be used alone, and the bis(aminophenoxy)benzene of the above formula (2) may be used alone or in combination with other aromatic diamines.

該溶媒可溶性聚醯亞胺，相對於來自其中包含之四元酸二酐之成份總量，來自於前述式(1)之氧基二苯二甲酸酐之成份較佳為含有至少30莫耳%以上、更佳為40至100莫耳%，殘餘份係其他芳香族四元酸二酐。 The solvent-soluble polyimine, the component derived from the oxydiphthalic anhydride of the above formula (1) preferably contains at least 30 mol%, based on the total amount of the component derived from the tetrabasic acid dianhydride contained therein. The above, more preferably 40 to 100 mol%, the residual part is another aromatic tetrabasic acid dianhydride.

此外，該溶媒可溶性聚醯亞胺，相對於來自其中包含之二胺之成份總量，來自於前述式(2)之雙(胺基苯氧基)苯之成份較佳為含有至少3至100莫耳%、更佳為4至100莫耳%、又更佳為5至100莫耳%、最佳為5至60莫耳%，殘餘份係其他芳香族二胺。 Further, the solvent-soluble polyimine, the component derived from the bis(aminophenoxy)benzene of the above formula (2) preferably contains at least 3 to 100, based on the total amount of the component derived from the diamine contained therein. The molar %, more preferably 4 to 100 mole %, still more preferably 5 to 100 mole %, most preferably 5 to 60 mole %, and the residual part is another aromatic diamine.

(a)此外，底覆樹脂(B)之一理想形態係在加成反應時一起併用式(2)之雙(胺基苯氧基)苯和由3,3’-二胺基-4,4’-二羥基二苯基醚、3,3’-二胺基-4,4’-二羥基二苯基碸、3,3’-二胺基-4,4’-二羥基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、2,2-雙(3-胺基-4-羥基苯基)丙烷、1,3- 六氟-2,2-雙(3-胺基-4-羥基苯基)丙烷、1,3-雙(4-胺基-3-羥基苯氧基)苯、9,9’-雙(3-胺基-4-羥基苯基)芴所組成群組選出至少1種之二胺基二酚類所得之聚醯亞胺，較佳為併用藉由單鍵而鍵結2分子單胺基單羥基苯之二胺基二羥基聯苯基，更佳為併用3,3’-二胺基-4,4’-二羥基聯苯基及/或3,3’-二羥基-4,4’-二胺基聯苯基。 (a) Further, one of the ideal forms of the undercoat resin (B) is a combination of the bis(aminophenoxy)benzene of the formula (2) and the 3,3'-diamino-4, in the addition reaction. 4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 3,3'-diamino-4,4'-dihydroxybiphenyl , 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3- Hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, 9,9'-bis (3) -Amino-4-hydroxyphenyl)indole consisting of a polyimine obtained by selecting at least one of the diaminodiphenols, preferably by bonding a single molecule of a monoamine group by a single bond Hydroxybenzene diaminodihydroxybiphenyl, more preferably 3,3'-diamino-4,4'-dihydroxybiphenyl and/or 3,3'-dihydroxy-4,4' - Diaminobiphenyl.

該等二胺基二酚類通常使用使底覆樹脂(B)之氫羥基當量計算值成為3,000g/eq.以下的量，較佳為2,000g/eq.以下之量。由於因後述之聚醯亞胺樹脂前驅物(C)之種類而使得起泡抑制效果不同，因此不一定限制在該範圍。該氫羥基當量可以是零。此外，理想範圍可以列舉500至2000g/eq.左右、更佳為1000至2000g/eq.左右。 The diaminodiphenol is usually used in an amount such that the calculated value of the hydrogen hydroxyl group equivalent of the undercoat resin (B) is 3,000 g/eq. or less, preferably 2,000 g/eq. or less. Since the foaming suppressing effect differs depending on the type of the polyimine resin precursor (C) to be described later, it is not necessarily limited to this range. The hydrogen hydroxyl equivalent can be zero. Further, the desirable range is about 500 to 2000 g/eq., more preferably about 1,000 to 2,000 g/eq.

相對於加成反應時使用二胺之總量，該等二胺基二酚類之使用量係2至40莫耳%左右、較佳為10至30莫耳%左右。殘餘份係前述式(2)之雙(胺基苯氧基)苯、或者是該雙(胺基苯氧基)苯與其他之芳香族二胺。 The amount of the diaminodiphenols used is about 2 to 40 mol%, preferably about 10 to 30 mol%, based on the total amount of the diamine used in the addition reaction. The residual component is bis(aminophenoxy)benzene of the above formula (2), or the bis(aminophenoxy)benzene and other aromatic diamines.

併用該等二胺基二酚類和前式(2)之雙(胺基苯氧基)苯而得之溶媒可溶性聚醯亞胺而使用作為底覆樹脂(B)，藉此可消除在聚醯亞胺樹脂前驅物(C)醯亞胺化時之起泡現象，該溶媒可溶性聚醯亞胺係理想之底覆樹脂(B)之一種。 The solvent-soluble polyimine obtained from the diaminodiphenols and the bis(aminophenoxy)benzene of the above formula (2) is used as the undercoat resin (B), whereby the aggregation can be eliminated. The bismuth imine resin precursor (C) is a foaming phenomenon in the case of imidization, and the solvent-soluble polyimine is one of the ideal base-coating resins (B).

(b)此外，底覆樹脂(B)之一種理想形態係在加成反應時，一起併用前式(2)之雙(胺基苯氧基)苯與和由可在各個苯環上分別具有1個甲基或三氟甲基之二胺基聯苯、可具有取代甲氧基之二胺基苯甲醯苯胺和3,7-二胺基-二甲基 二苯并噻吩所組成群組選出至少1種之芳香族二胺之形態也為理想形態之一種。該等芳香族二胺之結構式之具體例係顯示於後述式(11)。將併用該等二胺而得到之溶媒可溶性聚醯亞胺使用作為底覆樹脂(B)時，可得到蝕刻後捲曲小之覆銅積層板。在併用具有取代二甲基之二胺基聯苯或3,7-二胺基-二甲基二苯并噻吩時，常態剝離強度、耐熱及耐濕熱剝離強度係也維持1.00N/mm以上而非常良好。 (b) Further, an ideal form of the undercoat resin (B) is used in the addition reaction, and the bis(aminophenoxy)benzene of the above formula (2) is used together with and may have a respective benzene ring. a methyl or trifluoromethyldiaminobiphenyl, a diaminobenzilide anilide having a substituted methoxy group, and a 3,7-diamino-dimethyl group The form in which at least one aromatic diamine is selected from the group consisting of dibenzothiophene is also one of the ideal forms. Specific examples of the structural formula of the aromatic diamine are shown in the following formula (11). When the solvent-soluble polyimine obtained by using these diamines in combination is used as the undercoat resin (B), a copper-clad laminate having a small curl after etching can be obtained. When a diaminodiphenylbiphenyl or a 3,7-diamino-dimethyldibenzothiophene having a substituted dimethyl group is used in combination, the normal peel strength, heat resistance and wet heat peeling strength are maintained at 1.00 N/mm or more. Very good.

(c)此外，底覆樹脂(B)之一種理想形態係可以列舉一起併用式(2)之雙(胺基苯氧基)苯、以及前述(a)之二胺基二酚類和前述(b)所述之芳香族二胺之至少一種之形態。可以藉由併用兩者而消除起泡並減少捲曲。 (c) Further, a preferred form of the undercoat resin (B) may be a combination of the bis(aminophenoxy)benzene of the formula (2), and the diaminodiphenol of the above (a) and the foregoing ( b) a form of at least one of the aromatic diamines described. It is possible to eliminate foaming and reduce curl by using both.

(d)此外，底覆樹脂(B)之一種理想形態較佳為一起併用式(1)之氧基二苯二甲酸酐、和聯苯基四羧酸二酐或均苯四甲酸二酐作為四元酸二酐而得溶媒可溶性聚醯亞胺，並將該聚醯亞胺使用作為底覆樹脂(B)之本發明之覆銅積層板。此時也為蝕刻後捲曲小之覆銅積層板。 (d) Further, it is preferred that a preferred form of the undercoat resin (B) is used together with the oxydiphthalic anhydride of the formula (1), and the biphenyltetracarboxylic dianhydride or the pyromellitic dianhydride. The tetrabasic acid dianhydride is used to obtain a solvent-soluble polyimine, and the polyimine is used as the copper-clad laminate of the present invention as the undercoat resin (B). At this time, it is also a copper clad laminate having a small curl after etching.

由以上而得知：為了降低底覆樹脂(B)之線膨脹係數並得到覆銅積層板蝕刻後捲曲小之覆銅積層板，因此較佳為與一起併用前述式(2)之雙(胺基苯氧基)苯以及下列之式(11)所述之芳香族二胺而得到溶媒可溶性聚醯亞胺，並使用作為底覆樹脂(B)。 From the above, it is known that in order to reduce the linear expansion coefficient of the undercoat resin (B) and obtain a copper clad laminate having a small curl after etching of the copper clad laminate, it is preferred to use the bis (amine) of the above formula (2) together The benzyloxy)benzene and the aromatic diamine described in the following formula (11) are used to obtain a solvent-soluble polyimine and are used as the undercoat resin (B).

(R4係表示甲基，R5係同於前述而表示由氫原子、甲基、乙基、甲氧基、三氟甲基選出之官能基。) (R 4 represents a methyl group, and R 5 is the same as defined above and represents a functional group selected from a hydrogen atom, a methyl group, an ethyl group, a methoxy group or a trifluoromethyl group.)

相對於使用在加成反應之二胺之總莫耳數，該等芳香族二胺之使用量為0至95莫耳%、通常為10莫耳%以上、較佳為15至95莫耳%、更佳為25至85莫耳%。該等芳香族二胺成份之使用量過少時，恐怕會無法得到捲曲之抑制效果。 The aromatic diamine is used in an amount of from 0 to 95 mol%, usually 10 mol% or more, preferably 15 to 95 mol%, based on the total moles of the diamine used in the addition reaction. More preferably, it is 25 to 85 mol%. When the amount of the aromatic diamine component used is too small, the effect of suppressing curling may not be obtained.

此外，為了得到覆銅積層板蝕刻後之捲曲小之覆銅積層板，因此在加成反應時可一起併用前式(1)之氧基二苯二甲酸酐和前式(11)所述之四羧酸二酐(均苯四甲酸二酐或聯苯基四羧酸二酐)作為四羧酸二酐。 Further, in order to obtain a copper-clad laminate having a small curl after etching of the copper clad laminate, the oxydiphthalic anhydride of the above formula (1) and the former formula (11) may be used together in the addition reaction. Tetracarboxylic dianhydride (pyrenetetracarboxylic dianhydride or biphenyltetracarboxylic dianhydride) is used as the tetracarboxylic dianhydride.

相對於使用在加成反應之酸二酐之總莫耳數，該等併用之四羧酸二酐之使用量為0至70莫耳%、通常為20至70莫耳%、較佳為30至60莫耳%。殘餘份係通常為前式(1)之氧基二苯二甲酸酐。但是，可以在不妨礙本發明之範圍內併用其他芳香族四羧酸二酐。 The combined use of the tetracarboxylic dianhydride is from 0 to 70 mol%, usually from 20 to 70 mol%, preferably 30, relative to the total moles of the acid dianhydride used in the addition reaction. Up to 60% by mole. The residual moiety is usually the oxydiphthalic anhydride of the above formula (1). However, other aromatic tetracarboxylic dianhydrides may be used in combination without departing from the scope of the invention.

在不妨礙本發明之範圍內，也可在加成反應併用前述 之芳香族四元酸二酐和芳香族二胺以外之四元酸二酐及二胺。 In the range which does not hinder the present invention, it is also possible to carry out an addition reaction and use the aforementioned Aromatic tetrabasic acid dianhydride and tetrabasic acid dianhydride and diamine other than aromatic diamine.

具體地說，二胺化合物係可併用間苯二胺、對苯二胺、間甲苯二胺、4,4’-二胺基二苯基醚、3,3’-二甲基-4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基硫醚、3,3’-二甲基-4,4’-二胺基二苯基硫醚、3,3’-二乙氧基-4,4’-二胺基二苯基硫醚、3,3’-二胺基二苯基硫醚、4,4’-二胺基二苯甲酮、3,3’-二甲基-4,4’-二胺基二苯甲酮、3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、3,3’-二甲氧基-4,4’-二胺基二苯基硫醚、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(4-胺基苯基)丙烷、4,4’-二胺基二苯基亞碸、3,3’-二胺基二苯基碸、4,4’-二胺基二苯基碸、3,3’-二胺基聯苯、對二甲苯二胺、間二甲苯二胺、鄰二甲苯二胺、2,2’-雙(3-胺基苯氧基苯基)丙烷、2,2’-雙(4-胺基苯氧基苯基)丙烷、1,3-雙(4-胺基苯氧基苯基)苯、1,3’-雙(3-胺基苯氧基苯基)丙烷、雙(4-胺基-3-甲基苯基)甲烷、雙(4-胺基-3,5-二甲基苯基)甲烷、雙(4-胺基-3-乙基苯基)甲烷、雙(4-胺基-3,5-二乙基苯基)甲烷、雙(4-胺基-3-丙基苯基)甲烷、雙(4-胺基-3,5-二丙基苯基)甲烷、聚矽氧二胺、異佛爾酮二胺、六亞甲基二胺、三甲基六亞甲基二胺等，但是並非限定於該等。該等係可以1種或混合2種以上而使用。 Specifically, the diamine compound may be used in combination with m-phenylenediamine, p-phenylenediamine, m-toluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4. '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4' -diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4, 4'-Diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4' -diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 2,2' - bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylarylene, 3,3'-diamino Diphenyl hydrazine, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminobiphenyl, p-xylene diamine, m-xylene diamine, o-xylene diamine, 2, 2 '-Bis(3-Aminophenoxyphenyl)propane, 2,2'-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4-aminophenoxyphenyl) ) Benzene, 1,3'-double (3 -aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4- Amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane, bis (4 -Amino-3,5-dipropylphenyl)methane, polydecanediamine, isophoronediamine, hexamethylenediamine, trimethylhexamethylenediamine, etc., but not limited In these. These may be used alone or in combination of two or more.

只要不妨礙本發明，該等其他之二胺類之使用量並無特別限定，但是，相對於使用在加成反應之二胺類之總莫 耳數，通常為0至50莫耳%、較佳為0至40莫耳%。 The amount of the other diamines to be used is not particularly limited as long as it does not hinder the present invention, but is relative to the total amount of the diamines used in the addition reaction. The number of ears is usually from 0 to 50 mol%, preferably from 0 to 40 mol%.

前述式(1)之四元酸二酐以及記載於式(11)之四元酸二酐以外之四元酸二酐，係有乙二醇-雙(脫水偏苯三酸酯)、丙三醇-雙(脫水偏苯三酸酯)單乙酸酯、1,2,3,4-丁烷四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、2,2-雙(3,4-脫水二羧基苯基)丙烷、2,2-雙(3,4-脫水二羧基苯基)六氟丙烷、5-(2,5-二氧四氫-3-呋喃基)-3-甲基環己烯-1,2-二羧酸酐、3a,4,5,9b-四氫-5-(四氫-2,5-二氧-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮等，但是並非限定於該等。該等係可以使用1種，也可以混合2種以上而使用。 The tetrabasic acid dianhydride of the above formula (1) and the tetrabasic acid dianhydride other than the tetrabasic acid dianhydride of the formula (11) are ethylene glycol-bis(hydrogen trimellitate) and C3. Alcohol-bis(hydrogen trimellitate) monoacetate, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid Anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dehydrated dicarboxyphenyl)propane, 2,2-bis(3,4- Dehydrated dicarboxyphenyl)hexafluoropropane, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4, 5, 9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, etc., but is not limited thereto. These may be used alone or in combination of two or more.

在不妨礙本發明下該等其他之四元酸二酐之使用量並無特別限定，但是相對於使用在加成反應之酸二酐類之總莫耳數，通常為0至50莫耳%、較佳為0至40莫耳%。 The amount of the other tetrabasic acid dianhydride used is not particularly limited, and is usually from 0 to 50 mol% with respect to the total number of moles of the acid dianhydride used in the addition reaction. Preferably, it is 0 to 40% by mole.

整理本發明使用之溶媒可溶性聚醯亞胺之合成所使用之四元酸二酐和二胺之更佳之組合，係如下列之所述芳香族四羧酸二酐與芳香族二胺之組合。 A more preferred combination of the tetrabasic dianhydride and the diamine used in the synthesis of the solvent-soluble polyimine used in the present invention is a combination of an aromatic tetracarboxylic dianhydride and an aromatic diamine as described below.

芳香族四羧酸二酐係使用 Aromatic tetracarboxylic dianhydride

(i)式(1)之氧基二苯二甲酸二酐、或者是；(ii)由式(1)之氧基二苯二甲酸二酐和前述式(3)所表示之聯苯基四羧酸二酐及均苯四甲酸二酐所組成群組選出至少1種(較佳為聯苯基四羧酸二酐)， (i) an oxydiphthalic dianhydride of the formula (1) or (ii) an oxydiphthalic dianhydride of the formula (1) and a biphenyl group represented by the above formula (3) At least one selected from the group consisting of carboxylic acid dianhydride and pyromellitic dianhydride (preferably biphenyltetracarboxylic dianhydride),

芳香族二胺係使用 Aromatic diamine use

(iii)式(2)之雙(胺基苯氧基)苯和記載於前述式(4) 之芳香族二胺所組成群組選出至少1種之兩者。 (iii) bis(aminophenoxy)benzene of the formula (2) and described in the above formula (4) At least one of the group consisting of aromatic diamines is selected.

此外，更佳為使用前述(i)或(ii)作為芳香族四羧酸二酐，且併用(i)式(2)之雙(胺基苯氧基)苯、(ii)前述之二胺基二羧基聯苯基(較佳為3,3’-二胺基-4,4’-二羧基聯苯基)、以及(iii)由4,4’-二胺基-2,2’-二甲基(或者是三氟甲基)聯苯基、4,4’-二胺基-2’-甲氧基苯甲醯苯胺和3,7-二胺基-2,8-二甲基二苯并噻吩5,5-二氧化物所組成群組選出至少1種之3種之二胺而作為芳香族二胺時，特別佳為併用4,4’-二胺基-2,2’-二甲基聯苯基或3,7-二胺基-2,8-二甲基二苯并噻吩5,5-二氧化物而作為前述(iii)之二胺時。 Further, it is more preferred to use the above (i) or (ii) as the aromatic tetracarboxylic dianhydride, and to use (i) the bis(aminophenoxy)benzene of the formula (2), (ii) the aforementioned diamine a bis-carboxybiphenyl group (preferably 3,3'-diamino-4,4'-dicarboxybiphenyl), and (iii) from 4,4'-diamino-2,2'- Dimethyl (or trifluoromethyl)biphenyl, 4,4'-diamino-2'-methoxybenzimidil and 3,7-diamino-2,8-dimethyl When the dibenzothiophene 5,5-dioxide group is selected from the group consisting of at least one of three kinds of diamines, and as the aromatic diamine, it is particularly preferable to use 4,4'-diamino-2,2' together. - dimethylbiphenyl or 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide as the diamine of the above (iii).

本發明之底覆樹脂(B)層係藉由將包含溶解於溶媒之溶媒可溶性聚醯亞胺之樹脂清漆，塗佈在設置於銅箔(A)上之被覆層之表面，並進行乾燥而形成。該樹脂清漆之樹脂固態成份之濃度只要該樹脂清漆之黏度是適合於塗佈之黏度即可，由於使用之溶媒可溶性聚醯亞胺而不同，但是通常在溶媒中為5至50質量%、較佳為10至40質量%。在溶媒可溶性聚醯亞胺之合成結束後，在該聚醯亞胺溶解於溶媒時，可直接地使用該反應液而作為樹脂清漆。此外，可以依需要而濃縮該樹脂清漆或者是復加入溶媒來稀釋而使用。通常較佳為在可以溶解中間體之聚醯胺酸和閉環之溶媒可溶性聚醯亞胺(底覆樹脂(B))兩者之溶媒中進行前述之加成反應及脫水閉環反應。此種溶媒係可以列舉例如N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯 胺、N-甲基甲醯胺、γ-丁內酯、環戊酮及安息香酸甲酯等。因此，較佳為在含有例舉於此之溶媒所組成群組選出至少1種且可溶解前述聚醯胺酸和閉環之溶媒可溶性聚醯亞胺之溶媒中進行前述反應。 The undercoat resin (B) layer of the present invention is applied onto a surface of a coating layer provided on a copper foil (A) by drying a resin varnish containing a solvent-soluble polyimine dissolved in a solvent, and drying. form. The concentration of the resin solid component of the resin varnish may be as long as the viscosity of the resin varnish is suitable for coating, and is different from the solvent-soluble polyimine used, but it is usually 5 to 50% by mass in the solvent. Preferably, it is 10 to 40% by mass. After the completion of the synthesis of the solvent-soluble polyimine, when the polyimine is dissolved in a solvent, the reaction solution can be used as a resin varnish. Further, the resin varnish may be concentrated as needed or diluted by adding a solvent to be used. It is generally preferred to carry out the above-described addition reaction and dehydration ring-closure reaction in a solvent in which both the polylysine which can dissolve the intermediate and the solvent-soluble polyimine (the base resin (B)) which are ring-closed. Examples of such a solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamidine. Amine, N-methylformamide, γ-butyrolactone, cyclopentanone, and methyl benzoate. Therefore, it is preferred to carry out the above reaction in a solvent containing at least one selected from the group consisting of the solvents described above and capable of dissolving the polylysine and the ring-closed solvent-soluble polyimine.

較佳為在前述之加成反應時添加少量之吡啶而作為觸媒。此外，較佳為在脫水閉環反應時添加少量之甲苯、二甲苯、己烷、環己烷或庚烷等較低沸點之無極性溶媒而作為脫水劑，並一邊由反應系統除去反應時副生成物之水，一邊進行脫水反應。加成反應及脫水閉環反應時之反應溫度通常為150至220℃、較佳為180至200℃，反應時間通常為2至10小時、較佳為5至8小時。相對於反應液，觸媒之添加量通常為0.1至5質量%，相對於反應液，脫水劑之添加量通常為5至20質量%。 It is preferred to add a small amount of pyridine as a catalyst in the above-mentioned addition reaction. Further, it is preferred to add a small amount of a non-polar solvent such as toluene, xylene, hexane, cyclohexane or heptane as a dehydrating agent in the dehydration ring-closure reaction, and to generate a reaction by removing the reaction from the reaction system. The water of the object is dehydrated. The reaction temperature in the addition reaction and the dehydration ring closure reaction is usually from 150 to 220 ° C, preferably from 180 to 200 ° C, and the reaction time is usually from 2 to 10 hours, preferably from 5 to 8 hours. The amount of the catalyst added is usually from 0.1 to 5% by mass based on the reaction liquid, and the amount of the dehydrating agent added is usually from 5 to 20% by mass based on the reaction liquid.

本發明之底覆樹脂(B)係溶媒可溶性聚醯亞胺，因此可僅以將溶解該底覆樹脂之樹脂清漆塗佈於設置在銅箔(A)上之被覆層表面，之後藉由低處理溫度乾燥溶媒而形成底覆樹脂(B)層。因此，在本發明可容易地形成由聚醯亞胺而組成之底覆樹脂(B)層。 Since the undercoat resin (B) of the present invention is a solvent-soluble polyimine, the resin varnish in which the undercoat resin is dissolved can be applied only to the surface of the coating layer provided on the copper foil (A), and then low. The treatment solvent dries the solvent to form a primer resin (B) layer. Therefore, in the present invention, the undercoat resin (B) layer composed of polyimine can be easily formed.

在不損害設置在銅箔(A)上之被覆層及聚醯亞胺層(D)之接著強度之範圍內，則可以在本發明之底覆樹脂(B)加入各種之添加劑。該添加劑係列舉例如芳香族聚醯胺樹脂、環氧樹脂及酚樹脂等之有機添加劑、二氧化矽等之無機添加劑、顏料、染料、光暈(halation)防止劑、螢光增白劑、界面活性劑、調平劑(leveling agent)、塑化劑、阻燃劑、 抗氧化劑、填充劑、抗靜電劑、黏度調整劑、促進劑、光安定劑、光觸媒、低介電體、導電體、磁性體及熱分解性化合物等。 Various additives may be added to the undercoat resin (B) of the present invention insofar as the bonding strength of the coating layer and the polyimide layer (D) provided on the copper foil (A) is not impaired. Examples of the additive include organic polyamine resins, organic additives such as epoxy resins and phenol resins, inorganic additives such as cerium oxide, pigments, dyes, halation inhibitors, fluorescent whitening agents, and interfaces. Active agent, leveling agent, plasticizer, flame retardant, Antioxidants, fillers, antistatic agents, viscosity modifiers, accelerators, light stabilizers, photocatalysts, low dielectrics, electrical conductors, magnetic materials, and thermally decomposable compounds.

藉由在設置於無施行粗糙化處理之銅箔(A)上之被覆層之表面上，以使乾燥後厚度為1至5μm之方式塗佈包含底覆樹脂(B)之樹脂清漆並進行乾燥，藉此而得到底覆樹脂(B)層。例如藉由在被覆層上以使厚度為15μm之方式塗佈含有20質量%之底覆樹脂(B)之樹脂清漆，且通常在80至200℃、5至60分鐘，較佳為130至150℃、10至30分鐘而進行乾燥，藉此而得到大約3μm厚度之底覆層。乾燥時之熱源可以是熱風，也可以是遠紅外線加熱器，但是在防止氣化之溶媒滯留以及對樹脂內部實施加熱之方面來看，較佳為併用熱風和遠紅外線加熱器。 The resin varnish containing the undercoat resin (B) is applied and dried on the surface of the coating layer provided on the copper foil (A) which is not subjected to the roughening treatment so as to have a thickness of 1 to 5 μm after drying. Thereby, the undercoat resin (B) layer was obtained. For example, a resin varnish containing 20% by mass of the undercoat resin (B) is applied to the coating layer so as to have a thickness of 15 μm, and usually at 80 to 200 ° C, 5 to 60 minutes, preferably 130 to 150. Drying was carried out at ° C for 10 to 30 minutes, whereby a primer layer having a thickness of about 3 μm was obtained. The heat source during drying may be hot air or a far-infrared heater. However, in terms of preventing the retention of the vaporized solvent and heating the inside of the resin, it is preferred to use a hot air and a far-infrared heater in combination.

直接地接著於底覆樹脂(B)層上之聚醯亞胺層(D)係通常可藉由將形成於底覆樹脂(B)層上之含有聚醯胺酸之聚醯亞胺樹脂前驅物(C)層進行醯亞胺化而得到。此外，聚醯亞胺樹脂前驅物(C)層係通常較佳為藉由鑄模法而形成。 The polyimine layer (D) directly on the undercoat resin (B) layer can usually be preliminarily produced by a polyamidene-containing resin which is formed on the undercoat resin (B) layer. The layer (C) is obtained by imidization of ruthenium. Further, the polyimine resin precursor (C) layer is usually preferably formed by a molding method.

聚醯亞胺樹脂前驅物(C)層係可以藉由將四羧酸二酐與二胺，通常為芳香族四羧酸二酐與芳香族二胺在溶解聚醯胺酸之溶媒，例如N-甲基-2-吡咯烷酮或N,N-二甲基乙醯胺等之極性溶媒中進行反應而得到含有聚醯胺酸之反應液，使含有聚醯胺酸之反應液配合需要而調整樹脂濃度，而作為樹脂清漆塗佈於底覆樹脂(B)層上並進行乾燥，藉此而得到聚醯亞胺樹脂前驅物(C)層。得到之聚醯亞胺樹脂前 驅物(C)層藉由例如在250至400℃、5至20小時之條件下進行脫水閉環並聚醯亞胺化，而可成為具有接地接著於底覆樹脂(B)層之聚醯亞胺層(D)的本發明之覆銅積層板。 The polyimine resin precursor (C) layer can be obtained by dissolving a tetracarboxylic dianhydride with a diamine, usually an aromatic tetracarboxylic dianhydride and an aromatic diamine, in a solvent for dissolving the polyamic acid, such as N. - reacting in a polar solvent such as methyl-2-pyrrolidone or N,N-dimethylacetamide to obtain a reaction liquid containing polylysine, and adjusting the resin by mixing the reaction liquid containing polyglycine The resin varnish was applied onto the undercoat resin (B) layer and dried to obtain a polyimine resin precursor (C) layer. Before the obtained polyimine resin The drive (C) layer can be made into a polyfluorene having a grounding layer followed by a layer of the underlying resin (B) by, for example, performing dehydration ring closure and polyamidization at 250 to 400 ° C for 5 to 20 hours. A copper clad laminate of the present invention having an amine layer (D).

直接地接著於底覆樹脂(B)層之聚醯亞胺層(D)如果是使用在向來稱為2層CCL之覆銅積層板之聚醯亞胺層的話，任何一種都不會有特別之阻礙。 The polyimine layer (D) directly following the undercoat resin (B) layer is not particularly useful if it is used in a polyimide layer which is conventionally referred to as a two-layer CCL copper-clad laminate. Obstruction.

本發明之覆銅積層板之底覆樹脂(B)層上之聚醯亞胺層(D)，較佳為將如前述包含聚醯胺酸之聚醯亞胺樹脂前驅物(C)層進行加熱閉環而成為聚醯亞胺層(D)。 The polyimine layer (D) on the undercoat resin (B) layer of the copper-clad laminate of the present invention is preferably subjected to a polymethylene imide resin precursor (C) layer containing polyamic acid as described above. The ring is heated to form a polyimine layer (D).

聚醯亞胺樹脂前驅物(C)層係如果含有聚醯胺酸並可藉由加熱閉環而成為聚醯亞胺層(D)的話則皆可使用。 The polyimine resin precursor (C) layer can be used if it contains polyamic acid and can be made into a polyimine layer (D) by heating and ring closure.

例如聚醯亞胺樹脂前驅物(C)層係可為將包含作為樹脂成份之聚醯胺酸之樹脂清漆塗佈並乾燥而得者，並且也可為含有兩末端為胺基之下式(7)所示末端具有胺基之聚醯胺酸、以及下式(8)所示化合物的樹脂清漆塗佈並乾燥而得者。 For example, the polyimine resin precursor (C) layer may be obtained by coating and drying a resin varnish containing a polyamic acid as a resin component, and may also have an amine group having both ends ( 7) A resin varnish having an amine group having an amine group at the terminal and a resin varnish of the compound represented by the following formula (8) is coated and dried.

(式中，R6係表示4價之芳香族殘基，R7係表示2價之芳香族二胺殘基，x係平均重複數而表示1以上之實數。) (wherein R 6 represents a tetravalent aromatic residue, R 7 represents a divalent aromatic diamine residue, and x is an average repeat number and represents a real number of 1 or more.)

(式中，R8係表示4價之芳香族基，R9係表示氫原子或C1至C3烷基。) (wherein R 8 represents a tetravalent aromatic group, and R 9 represents a hydrogen atom or a C1 to C3 alkyl group.)

本發明中較佳為後者。 The latter is preferred in the present invention.

後者之情形所得到之聚醯亞胺樹脂前驅物(C)層較佳為包含前述式(7)所表示末端具有胺基之聚醯胺酸以及式(8)所表示之化合物。 The polyimine resin precursor (C) layer obtained in the latter case preferably comprises a polylysine having an amine group at the terminal represented by the above formula (7) and a compound represented by the formula (8).

聚醯亞胺樹脂前驅物(C)層中之聚醯胺酸含有量較佳為80至100質量%、更佳為90至99質量%，可以在殘餘份含有在使用作為原料之四羧酸二酐上以水或C1至C3醇進行加成開環而產生之四羧酸或/及其酯。 The polyphthalamide content in the polyimine resin precursor (C) layer is preferably from 80 to 100% by mass, more preferably from 90 to 99% by mass, and may be contained in the residue as a tetracarboxylic acid as a raw material. The tetracarboxylic acid or/and its ester produced by the addition of a dianhydride to water or a C1 to C3 alcohol.

此外，聚醯胺酸為式(7)所示化合物時，較佳為在聚醯亞胺樹脂前驅物(C)層中包含式(8)所示之化合物。此時聚醯亞胺樹脂前驅物(C)層中之聚醯胺酸含有量較佳為80至100質量%、更佳為90至99質量%。殘餘份係式(8)所示之化合物，也可包含微量溶媒等。此外，此時式(7)之R6之4價之芳香族基和R8之4價之芳香族基係可以相同，也可以不同，但是通常較佳為相同。 Further, when the polyglycolic acid is a compound represented by the formula (7), it is preferred to include a compound represented by the formula (8) in the polyimine resin precursor (C) layer. The polyamine acid content in the polyimine resin precursor (C) layer at this time is preferably from 80 to 100% by mass, more preferably from 90 to 99% by mass. The compound represented by the formula (8) may also contain a trace amount of a solvent or the like. Further, in this case, the tetravalent aromatic group of R 6 of the formula (7) and the tetravalent aromatic group of R 8 may be the same or different, but are usually preferably the same.

前述之樹脂清漆可使用在覆銅積層板用之習知之聚醯胺酸樹脂清漆、或市面販賣之聚醯胺酸樹脂清漆。後者之 聚醯胺酸樹脂清漆之市售品係列舉KAYAFLEX KPI-126(日本化藥股份有限公司製)等。後者之聚醯胺酸樹脂清漆之情形，相對於來自所得之聚醯亞胺中之四羧酸成份之總量，以3至20莫耳%左右之比例而含有末端具有胺基之聚醯胺酸、以及在四羧酸二酐以甲醇、乙醇等C1至C3醇或/及水反應而得之式(8)所示化合物。認為在該樹脂清漆或聚醯亞胺樹脂前驅物(C)層中，該式(8)所示之化合物係與式(7)之聚醯胺酸形成鹽。因此，認為在後者之情形為該鹽和聚醯胺酸樹脂之混合物。 The above-mentioned resin varnish can be used as a conventional polyamic acid varnish for use in a copper clad laminate, or a commercially available polyamic acid varnish. The latter A commercially available product series of polyacetic acid resin varnish is KAYAFLEX KPI-126 (manufactured by Nippon Kayaku Co., Ltd.). In the case of the latter polyamic acid resin varnish, the polyamine having an amine group at the end is contained in a ratio of about 3 to 20 mol% with respect to the total amount of the tetracarboxylic acid component in the obtained polyimine. The acid and the compound of the formula (8) obtained by reacting a tetracarboxylic dianhydride with a C1 to C3 alcohol such as methanol or ethanol or/and water. It is considered that the compound represented by the formula (8) forms a salt with the polylysine of the formula (7) in the resin varnish or the polyimide intermediate resin precursor (C) layer. Therefore, it is considered that in the latter case, a mixture of the salt and the polyamic acid resin.

此外，成為聚醯亞胺樹脂前驅物(C)之原料之四羧酸二酐和二胺之組合無任何限制，如果是向來習知之CCL用聚醯亞胺樹脂之合成所使用之四羧酸二酐和二胺之組合的話則皆可使用。 Further, the combination of the tetracarboxylic dianhydride and the diamine which are the raw materials of the polyimine resin precursor (C) is not limited, and is a tetracarboxylic acid used for the synthesis of a conventional polycyanimide resin for CCL. A combination of a dianhydride and a diamine can be used.

在本發明之覆銅積層板中，底覆樹脂(B)層和設置於銅箔(A)上之被覆層之界面、以及底覆樹脂(B)層和直接地接著於該底覆樹脂層之聚醯亞胺層之界面之接著強度在通常(溫度大約25℃)之氛圍下係當然，即使在150℃左右之高溫條件下例如保持168小時後、或者是在40℃、濕度95%(表示為95% RH)等之高溫高濕度條件下例如保持96小時後，在實用上較佳為0.8N/mm以上、更佳為1.0N/mm以上。上限係並無特定，但通常為2N/mm。 In the copper clad laminate of the present invention, the interface between the undercoat resin (B) layer and the coating layer provided on the copper foil (A), and the undercoat resin (B) layer and directly on the underlying resin layer The bonding strength of the interface of the polyimide layer is, in general, an atmosphere (temperature of about 25 ° C), of course, even under high temperature conditions of about 150 ° C, for example, after 168 hours, or at 40 ° C, humidity of 95% ( It is practically preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more after high-temperature and high-humidity conditions, such as 95% RH). The upper limit is not specific, but is usually 2N/mm.

可以藉由在本發明之覆銅積層板進行打穿、蝕刻、開孔、電鍍等之加工而得到本發明之可撓性印刷電路基板用之配線板。 The wiring board for a flexible printed circuit board of the present invention can be obtained by performing processing such as punching, etching, opening, plating, or the like on the copper clad laminate of the present invention.

本發明之理想之覆銅積層板係可以列舉下列者。 Preferred copper-clad laminates of the present invention include the following.

(I)一種覆銅積層板，係前述本發明(解決前述課題之手段之項目中第1至3項中任一項所述之發明)之覆銅積層板，其中，相對於來自前述溶媒可溶性聚醯亞胺中的四元酸二酐之成份之總量，而包含來自於前述式(1)所示之氧基二苯二甲酸酐之成份30莫耳%以上、較佳為40至100莫耳%，殘餘份係來自其他芳香族四元酸二酐之成份，相對於來自前述溶媒可溶性聚醯亞胺中的二胺之成份之總量，而包含來自於前式(2)所示之雙(胺基苯氧基)苯之成份3至100莫耳%、較佳為4至100莫耳%、更佳為5至60莫耳%，殘餘份係來自於其他芳香族二胺之成份。 (I) A copper-clad laminate which is a copper-clad laminate according to any one of the first to third aspects of the invention of the present invention, wherein the solvent is soluble from the solvent The total amount of the components of the tetrabasic acid dianhydride in the polyimine, and the composition of the oxydiphthalic anhydride represented by the above formula (1) is 30 mol% or more, preferably 40 to 100. Mol%, the residual component is derived from other aromatic tetrabasic acid dianhydride, relative to the total amount of the component of the diamine from the solvent-soluble polyimine, and is contained from the formula (2) The bis(aminophenoxy)benzene component has a composition of from 3 to 100 mol%, preferably from 4 to 100 mol%, more preferably from 5 to 60 mol%, and the residual portion is derived from other aromatic diamines. Ingredients.

(II)前述(I)所述之覆銅積層板，其中，在前述芳香族四元酸二酐和前述芳香族二胺反應時，前述其他芳香族二胺係至少併用前述二胺基二酚類而得到之聚醯亞胺。 (II) The copper-clad laminate according to the above (I), wherein, when the aromatic tetrabasic dianhydride is reacted with the aromatic diamine, the other aromatic diamine is at least used in combination with the aforementioned diaminodiphenol. Polyimine obtained in a class.

(III)前述(II)所述之覆銅積層板，其中，前述二胺基二酚類為二胺基二羥基聯苯。 (III) The copper clad laminate according to the above (II), wherein the diaminodiphenol is diaminodihydroxybiphenyl.

(IV)前述(II)所述之覆銅積層板，其中，前述二胺基二酚類為3,3’-二胺基-4,4’-二羥基聯苯。 (II) The copper clad laminate according to the above (II), wherein the diaminodiphenol is 3,3'-diamino-4,4'-dihydroxybiphenyl.

(V)前述(II)至(IV)中任一項所述之覆銅積層板，其中，相對於芳香族二胺之總量，前述二胺基二酚類之使用量為2至40莫耳%左右、較佳為10至30莫耳%左右。 The copper-clad laminate according to any one of the above-mentioned (II), wherein the amount of the diaminodiphenol used is 2 to 40 moles based on the total amount of the aromatic diamine. The ear is about %, preferably about 10 to 30 mol%.

(VI)前述(I)至(IV)中任一項所述之覆銅積層板，其中，溶媒可溶性聚醯亞胺之羥基當量為1000至2000g/eq。 (VI) The copper clad laminate according to any one of the above (1) to (IV) wherein the solvent-soluble polyimine has a hydroxyl equivalent of from 1,000 to 2,000 g/eq.

(VII)前述(II)至(IV)中任一項所述之覆銅積層板，其中，前述之溶媒可溶性聚醯亞胺為併用作為上述其他芳香族二胺之由4,4’-二胺基-2,2’-二甲基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、4,4’-二胺基-2’-甲氧基苯甲醯苯胺和3,7-二胺基-2,8-二甲基二苯并噻吩5,5-二氧化物所組成群組選出至少1種而得到之聚醯亞胺。 The copper-clad laminate according to any one of the above-mentioned (II), wherein the solvent-soluble polyimine is used in combination as the other aromatic diamine 4,4'-di Amino-2,2'-dimethylbiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2'- A polyimine obtained by selecting at least one of a group consisting of methoxybenzidine anilide and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide.

(VIII)前述(VII)所述之覆銅積層板，其中，前述(VII)所述之其他芳香族二胺之至少1種為4,4’-二胺基-2,2’-二甲基聯苯或3,7-二胺基-2,8-二甲基二苯并噻吩5,5-二氧化物，更佳為4,4’-二胺基-2,2’-二甲基聯苯。 (C) The copper-clad laminate according to the above (VII), wherein at least one of the other aromatic diamines described in the above (VII) is 4,4'-diamino-2,2'-dimethyl Biphenyl or 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide, more preferably 4,4'-diamino-2,2'-dimethyl Base benzene.

(IX)前述(VI)至(VIII)中任一項所述之覆銅積層板，其中，相對於芳香族二胺之總量，前述其他芳香族二胺之使用量為0至96莫耳%、較佳為40至95莫耳%。 The copper-clad laminate according to any one of the above-mentioned (VI), wherein the other aromatic diamine is used in an amount of from 0 to 96 mol per mol of the total amount of the aromatic diamine. %, preferably 40 to 95% by mole.

(X)前述(VII)至(IX)中任一項所述之覆銅積層板，其中，前述溶媒可溶性聚醯亞胺係在加成反應時一起併用前式(2)所示之雙(胺基苯氧基)苯、與前述二胺基二酚類和前述(VII)所述之其他芳香族二胺之至少1種而得到之聚醯亞胺。 The copper-clad laminate according to any one of the above-mentioned (VII), wherein the solvent-soluble polyimine is used together with the double (Formula (2)) in the addition reaction. A polyimine obtained by at least one of an aminophenoxy)benzene and the above-described diaminodiphenol and the other aromatic diamine described in the above (VII).

(XI)前述(VII)所述之覆銅積層板，其中，相對於芳香族二胺之總量，前述(VII)所述其他芳香族二胺之至少1種之使用量為4至94莫耳%、較佳為40至95莫耳%。 (II) The copper-clad laminate according to the above (VII), wherein at least one of the other aromatic diamines described in the above (VII) is used in an amount of from 4 to 94 mol% based on the total amount of the aromatic diamine. Ear %, preferably 40 to 95 mole %.

(XII)前述(I)至(X)中任一項所述之覆銅積層板，其中，前述溶媒可溶性聚醯亞胺為一起併用前述式(1)所示氧基二苯二甲酸酐、與前述式(3)所示之聯苯基四羧酸二酐和 均苯四甲酸二酐所組成群組選出至少1種作為四元酸二酐而得到之聚醯亞胺。 The copper-clad laminate according to any one of the above-mentioned (1), wherein the solvent-soluble polyimine is used together with the oxydiphthalic anhydride represented by the above formula (1). And biphenyltetracarboxylic dianhydride represented by the above formula (3) At least one polyimine obtained as a tetrabasic dianhydride is selected from the group consisting of pyromellitic dianhydride.

(XIII)前述(XII)所述之覆銅積層板，，其中，由前述式(3)所示之聯苯基四羧酸二酐和均苯四甲酸二酐所組成群組選出至少1種係聯苯基四羧酸二酐。 (XIII) The copper-clad laminate according to the above (XII), wherein at least one selected from the group consisting of biphenyltetracarboxylic dianhydride and pyromellitic dianhydride represented by the above formula (3) A biphenyltetracarboxylic dianhydride.

(XIV)前述(XII)或(XIII)所述之覆銅積層板，其中，相對於四元酸二酐之總量，由前述式(3)所示聯苯基四羧酸二酐和均苯四甲酸二酐所組成群組選出至少1種之使用量為0至70莫耳%、較佳為30至60莫耳%。 (XIV) The copper-clad laminate according to the above (XII) or (XIII), wherein the biphenyltetracarboxylic dianhydride and the both are represented by the above formula (3) with respect to the total amount of the tetrabasic dianhydride At least one selected from the group consisting of pyromellitic dianhydride is used in an amount of from 0 to 70 mol%, preferably from 30 to 60 mol%.

(XV)前述(I)至(XIV)中任一項所述之覆銅積層板，其中，聚醯亞胺層(D)為將包含對應之聚醯胺酸之聚醯亞胺樹脂前驅物(C)層藉由加熱醯亞胺化而得到之聚醯亞胺層(D)。 The copper-clad laminate according to any one of the above-mentioned (I) to (XI), wherein the polyimine layer (D) is a polyimine resin precursor containing a corresponding poly-proline (C) A layer of polyimine (D) obtained by heating a hydrazine imidization.

(XVI)前述(XV)所述之覆銅積層板，其中，包含聚醯胺酸之聚醯亞胺樹脂前驅物(C)層係含有80至100質量%之聚醯胺酸且含有0至20質量%之前述式(8)所示之四羧酸衍生物之聚醯亞胺樹脂前驅物(C)層。 (XVI) The copper-clad laminate according to the above (XV), wherein the poly(imine) resin precursor (C) layer comprising poly-proline contains 80 to 100% by mass of polyamic acid and contains 0 to 20% by mass of the poly(arylenemine resin) precursor (C) layer of the tetracarboxylic acid derivative represented by the above formula (8).

(XVII)前述(I)至(XVI)中任一項所述之覆銅積層板，其中，被覆層之Ni被覆量為每dm2為15μg以上、未滿300μg。 The copper-clad laminate according to any one of the above-mentioned (I), wherein the coating layer has a Ni coating amount of 15 μg or more and less than 300 μg per dm 2 .

(XVIII)前述(XVII)所述之覆銅積層板，其中，被覆層之Ni被覆量為20至200μg/dm2。 (XVIII) The copper clad laminate according to the above (XVII), wherein the coating layer has a Ni coating amount of 20 to 200 μg/dm 2 .

(XIX)前述(I)至(XVIII)中任一項所述之覆銅積層板，其中，以Ni被覆量來作為基準(質量)，被覆層之Cr 被覆量之比例為多於0.5、小於1。 (C) The copper-clad laminate according to any one of the above-mentioned (I), wherein the Cr coating layer is used as a reference (mass) based on the Ni coating amount. The ratio of the amount of coating is more than 0.5 and less than 1.

(XX)前述(I)至(XIX)中任一項所述之覆銅積層板，其中，具有滿足前述(1)至(3)條件之被覆層且無施行粗糙化處理之銅箔(A)和直接接著於該被覆層之底覆層樹脂(B)層之間之常態剝離強度為0.8N/mm以上。 (C) The copper clad laminate according to any one of the above (1) to (3), wherein the copper foil having the coating layer satisfying the conditions (1) to (3) and not subjected to the roughening treatment (A) And the normal peeling strength between the layer of the undercoat resin (B) directly following the coating layer is 0.8 N/mm or more.

(XXI)前述(XX)所述之覆銅積層板，其中，該常態剝離強度為1.0N/mm以上。 (XXI) The copper clad laminate according to the above (XX), wherein the normal peel strength is 1.0 N/mm or more.

此外，在前述各項目中，記載為較佳或更佳等時，某一項目較佳形態與其他項目組合之形態、或者是將各項目較佳形態彼此組合之形態、將更佳形態和其他項目之較佳形態組合之形態，係皆為本發明較佳形態之一。 In addition, in each of the above items, when it is described as preferred or better, the form of the preferred form of one item is combined with the other items, or the form in which the preferred forms of each item are combined with each other, the form and the other form are better. The form of the preferred combination of the items is one of the preferred forms of the invention.

(實施例) (Example)

以下藉由合成例及實施例而更詳細地說明本發明，但是本發明係並非限定於該等實施例。 Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited to the Examples.

製作例1(使用於本發明之具有被覆層之銅箔(A)之製作) Production Example 1 (Production of Copper Foil (A) with Coating Layer Used in the Present Invention)

銅箔基材係使用無粗糙化處理之壓延銅箔(JX日鑛日石金屬股份有限公司製之C1100、厚度18μm、表面粗糙度(Rz)0.7μm)，在藉由Ar離子槍而由該銅箔之單面除去預已附著之薄氧化膜之後，藉由連續濺鍍裝置而依序成膜，並使Ni層及Cr層分別為1nm之厚度。Ni及Cr之各個之被覆量係Ni：85μg/dm2及Cr：70μg/dm2。此外，合併Ni層及Cr層之被覆層之厚度最大值係2.1nm，最小值係1.9nm(最小值相對於最大值之比例：大約90%)。以該得到之銅箔作為A-1。 The copper foil substrate was a rolled copper foil (J1 Nippon Mining & Metal Co., Ltd. C1100, thickness 18 μm, surface roughness (Rz) 0.7 μm) which was not roughened, and was used by an Ar ion gun. After removing the pre-adhered thin oxide film on one side of the copper foil, the film was sequentially formed by a continuous sputtering apparatus, and the Ni layer and the Cr layer were each made to have a thickness of 1 nm. The coating amount of each of Ni and Cr was Ni: 85 μg/dm 2 and Cr: 70 μg/dm 2 . Further, the maximum thickness of the coating layer in which the Ni layer and the Cr layer are combined is 2.1 nm, and the minimum value is 1.9 nm (ratio of the minimum value to the maximum value: about 90%). The obtained copper foil was designated as A-1.

此外，氧化膜之除去條件及濺鍍之條件、被覆量之測定方法及被覆層之厚度測定係如下述。 Further, the conditions for removing the oxide film, the conditions for sputtering, the method for measuring the amount of coating, and the thickness of the coating layer are as follows.

＊氧化膜之除去條件及濺鍍之條件 * Removal conditions of oxide film and conditions of sputtering

˙裝置：連續濺鍍裝置(ULVAC股份有限公司製) ̇ device: continuous sputtering device (manufactured by ULVAC Co., Ltd.)

Ar離子槍(Advanced Energy股份有限公司製) Ar ion gun (manufactured by Advanced Energy Co., Ltd.)

˙離子槍電力：600W ̇Ion gun power: 600W

˙離子槍Ar氣體壓力：6.0×10-2Pa Helium ion gun Ar gas pressure: 6.0 × 10 -2 Pa

˙濺鍍Ar氣體壓力：0.3Pa ̇ Sputtering Ar gas pressure: 0.3Pa

˙達到真空度：1.0×10-5Pa ̇Achieve vacuum: 1.0×10 -5 Pa

˙標靶：Ni層用=Ni(純度3N) ̇ target: Ni layer = Ni (purity 3N)

Cr層用=Cr(純度3N) Cr layer = Cr (purity 3N)

˙濺鍍電力：Ni 1.9kW、Cr 1.8kW ̇Sputtering power: Ni 1.9kW, Cr 1.8kW

＊被覆量之測定 *Measurement of coverage

將50mm×50mm之銅箔表面皮膜溶解於混合HNO3(2重量%)和HCl(5重量%)之溶液，藉由ICP發光光譜分析裝置(SII奈米科技股份有限公司製、SFC-3100)而定量其溶液中之金屬濃度，算出每單位面積之金屬量(μg/dm2)。 A 50 mm × 50 mm copper foil surface film was dissolved in a solution of mixed HNO 3 (2% by weight) and HCl (5% by weight) by an ICP emission spectrometer (SII-3100, SFC-3100) The metal concentration in the solution was quantified, and the amount of metal per unit area (μg/dm 2 ) was calculated.

＊被覆層之厚度測定 *Measurement of thickness of coating

以下表示在藉由穿透型電子顯微鏡(TEM)而觀察被覆層時之TEM之測定條件。由拍攝於觀察視野中之被覆層整體而任意地選擇幅寬50nm之被覆層，測定其50nm間之厚度之最大值及最小值。任意地選擇3視野而進行該測定， 並求出製作之銅箔之被覆層厚度之最大值及最小值。此外，就被覆層之厚度而言，以百分比求出最小值相對於最大值之比例。 The measurement conditions of the TEM when the coating layer is observed by a transmission electron microscope (TEM) are shown below. A coating layer having a width of 50 nm was arbitrarily selected from the entire coating layer taken in the observation field, and the maximum and minimum values of the thickness between 50 nm were measured. The measurement is performed by arbitrarily selecting 3 fields of view, The maximum and minimum values of the thickness of the coating layer of the produced copper foil were determined. Further, in terms of the thickness of the coating layer, the ratio of the minimum value to the maximum value is obtained as a percentage.

TEM之測定條件 TEM measurement conditions

˙裝置：TEM(日立製作所股份有限公司製、型式：H9000NAR) ̇ device: TEM (made by Hitachi, Ltd., type: H9000NAR)

˙加速電壓：300kV ̇ Acceleration voltage: 300kV

˙倍率：300000倍 ̇ magnification: 300,000 times

˙觀察視野：60nm×60nm ̇ Observation field: 60nm × 60nm

製作例2(藉由電鍍法而形成被覆層之比較用之銅箔之製作) Production Example 2 (Production of Copper Foil for Comparative Coating Layer Formed by Electroplating)

銅箔基材係使用無粗糙化處理之壓延銅箔(JX日鑛日石金屬股份有限公司製之C1100、厚度18μm、表面粗糙度(Rz)0.7μm)，按照製作例1之方法而藉著Ar離子槍而由該銅箔之單面除去預已附著之薄氧化膜之後，依序地施行Ni電鍍及鉻酸鹽處理而使得Ni層及Cr層分別為平均約1nm之厚度。合併Ni層及Cr層之被覆層之厚度最大值係3.0nm，最小值係0.5nm。以該銅箔，作為A-2。 The copper foil substrate was a rolled copper foil (C1100, thickness 18 μm, surface roughness (Rz) 0.7 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) without roughening, and was passed according to the method of Production Example 1. After the Ar ion gun was used to remove the pre-adhered thin oxide film from one side of the copper foil, Ni plating and chromate treatment were sequentially performed so that the Ni layer and the Cr layer each had an average thickness of about 1 nm. The thickness of the coating layer in which the Ni layer and the Cr layer were combined was 3.0 nm in maximum, and the minimum value was 0.5 nm. This copper foil was used as A-2.

此外，Ni電鍍及鉻酸鹽處理之條件係如下述。 Further, the conditions of Ni plating and chromate treatment are as follows.

(1)Ni電鍍 (1) Ni plating

˙電鍍浴：胺基磺酸鎳(Ni2+為110g/L)、H3BO3(40g/L) ̇Electroplating bath: nickel sulfonate (Ni 2+ 110g / L), H 3 BO 3 (40g / L)

˙電流密度：1.0A/dm2 ̇ current density: 1.0A/dm 2

˙浴溫：55℃ Bath temperature: 55 ° C

˙Ni量：95μg/dm2(厚度大約1.1nm) ̇Ni amount: 95 μg / dm 2 (thickness about 1.1 nm)

(2)鉻酸鹽處理 (2) chromate treatment

˙電鍍浴：CrO3(1g/L)、Zn(粉末0.4g)、Na2SO4(10g/L) ̇Electroplating bath: CrO 3 (1g/L), Zn (powder 0.4g), Na 2 SO 4 (10g/L)

˙電流密度：2.0A/dm2 ̇ current density: 2.0A/dm 2

˙浴溫：55℃ Bath temperature: 55 ° C

˙Cr量：70μg/dm2(與製作例1幾乎同量之Cr量) ̇Cr amount: 70 μg/dm 2 (amount of Cr almost the same as in Production Example 1)

合成例1 Synthesis Example 1

在附有溫度計、迴流冷卻器、迪安-斯塔克(Dean-Stark)裝置、粉體導入口、氮導入裝置及攪拌裝置之500ml之反應器中，加入作為二胺化合物之APB-N(1,3-雙-(3-胺基苯氧基)苯、三井化學股份有限公司製、分子量292.33)51.49g(0.176莫耳)以及作為溶劑之N-甲基-2-吡咯烷酮79.65g，一邊流動乾燥氮一邊在70℃攪拌30分鐘。然後添加作為四羧酸二酐之ODPA(4,4’-氧基二苯二甲酸酐、Manac股份有限公司製、分子量310.22)55.73g(0.180莫耳)、作為溶劑之N-甲基-2-吡咯烷酮119.47g、作為觸媒之吡啶2.84g以及作為脫水劑之甲苯37.99g，並將反應器內升溫至180℃為止。一邊使用迪安-斯塔克裝置除去由於醯亞胺化反應而產生之水，一邊在180℃進行3小時之加熱閉環反應之後，復在相同溫度進行加熱2小時而除去吡啶及甲苯。反應結束後，將冷卻至80℃以下之反應液使用孔徑3μm之鐵氟隆(註冊商標)製之過濾器而施行加壓過濾，藉此而得到含有34質量%聚醯亞胺之底覆層樹脂清漆(以下為B-1。)300g。底覆層樹脂之數平均分子量係9,900，重量平均分子量係54,000(皆根據凝膠滲透色譜法之測定結果而以聚苯乙烯換算算出。以下相同。)。 APB-N as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder introduction port, a nitrogen introduction device, and a stirring device. 1,3-bis-(3-aminophenoxy)benzene, manufactured by Mitsui Chemicals Co., Ltd., molecular weight 292.33) 51.49 g (0.176 mol), and N-methyl-2-pyrrolidone 79.65 g as a solvent The flowing dry nitrogen was stirred at 70 ° C for 30 minutes. Then, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22), 55.73 g (0.180 mol) as a tetracarboxylic dianhydride, and N-methyl-2 as a solvent were added. 119.47 g of pyrrolidone, 2.84 g of pyridine as a catalyst, and 37.99 g of toluene as a dehydrating agent, and the temperature in the reactor was raised to 180 °C. While removing water due to the hydrazine imidization reaction using a Dean-Stark apparatus, the mixture was heated at a temperature of 180 ° C for 3 hours, and then heated at the same temperature for 2 hours to remove pyridine and toluene. After the completion of the reaction, the reaction liquid cooled to 80 ° C or lower was subjected to pressure filtration using a filter made of Teflon (registered trademark) having a pore size of 3 μm, thereby obtaining a primer layer containing 34% by mass of polyimine. Resin varnish (hereinafter B-1.) 300 g. The number average molecular weight of the undercoat resin was 9,900, and the weight average molecular weight was 54,000 (all calculated in terms of polystyrene according to the measurement results by gel permeation chromatography. The same applies hereinafter).

合成例2 Synthesis Example 2

在附有溫度計、迴流冷卻器、迪安-斯塔克裝置、粉體導入口、氮導入裝置及攪拌裝置之500ml之反應器中，加入作為二胺化合物之APB-N(1,3-雙-(3-胺基苯氧基)苯、三井化學股份有限公司製、分子量292.33)30.02g(0.103莫耳)、HAB(3,3’-二胺基-4,4’-二氧聯苯、日本化藥股份有限公司製、分子量216.24)4.85g(0.022莫耳)以及作為溶劑之N-甲基-2-吡咯烷酮64.76g，一邊流動乾燥氮，一邊在70℃攪拌30分鐘。然後，添加作為四羧酸二酐之ODPA(4,4’-氧基二苯二甲酸酐、Manac股份有限公司製、分子量310.22)36.62g(0.118莫耳)、作為溶劑之N-甲基-2-吡咯烷酮68.00g、作為觸媒之吡啶1.87g以及作為脫水劑之甲苯28.55g，將反應器內升溫至180℃為止。一邊使用迪安-斯塔克裝置除去由於醯亞胺化反應而產生之水，一邊在180℃進行3小時之加熱閉環反應之後，復在相同溫度下進行加熱2小時而除去吡啶及甲苯。在反應結束後，將冷卻至80℃以下之反應液使用孔徑3μm之鐵氟隆(註冊商標)製之過濾器施行加壓過濾，藉此而得到含有34質量%聚醯亞胺之底覆層樹脂清漆(以下為B-2。)200g。底覆層樹脂之數平均分子量係10,500，重量平均分子量係36,400。由原料加入量而算出之理論羥基當量係1500g/eq.。 In a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder introduction port, a nitrogen introduction device, and a stirring device, APB-N (1,3-double) as a diamine compound was added. -(3-Aminophenoxy)benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.02 g (0.103 mol), HAB (3,3'-diamino-4,4'-dioxybiphenyl The product was prepared by Nippon Kayaku Co., Ltd., molecular weight 216.24), 4.85 g (0.022 mol), and 64.76 g of N-methyl-2-pyrrolidone as a solvent, and the mixture was stirred at 70 ° C for 30 minutes while flowing nitrogen. Then, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22) 36.62 g (0.118 mol) as a tetracarboxylic dianhydride, and N-methyl group as a solvent were added. 68.00 g of 2-pyrrolidone, 1.87 g of pyridine as a catalyst, and 28.55 g of toluene as a dehydrating agent were heated to 180 ° C in the reactor. While removing water due to the hydrazine imidization reaction using a Dean-Stark apparatus, heating and ring closure reaction was carried out at 180 ° C for 3 hours, and then heating was carried out at the same temperature for 2 hours to remove pyridine and toluene. After the completion of the reaction, the reaction liquid cooled to 80 ° C or lower was subjected to pressure filtration using a filter of Teflon (registered trademark) having a pore size of 3 μm, thereby obtaining a primer layer containing 34% by mass of polyimine. Resin varnish (hereinafter B-2.) 200g. The undercoat resin had a number average molecular weight of 10,500 and a weight average molecular weight of 36,400. The theoretical hydroxyl equivalent calculated from the amount of the raw material added was 1500 g/eq.

合成例3 Synthesis Example 3

在附有溫度計、迴流冷卻器、迪安-斯塔克裝置、粉體導入口、氮導入裝置及攪拌裝置之500ml之反應器中，加 入作為二胺化合物之APB-N(1,3-雙-(3-胺基苯氧基)苯、三井化學股份有限公司製、分子量292.33)1.08g(0.003莫耳)、m-TBHG(4,4’-二胺基-2,2’-二甲基聯苯、和哥山精化股份有限公司製、分子量212.29)7.04g(0.033莫耳)、HAB(3,3’-二胺基-4,4’-二羥基聯苯、日本化藥股份有限公司製、分子量216.24)1.53g(0.007莫耳)以及作為溶劑之N-甲基-2-吡咯烷酮54.68g，一邊流動乾燥氮一邊在70℃攪拌30分鐘。然後添加作為四羧酸二酐之ODPA(4,4’-氧基二苯二甲酸酐、Manac股份有限公司製、分子量310.22)8.02g(0.026莫耳)、BPDA(3,3’,4,4’-聯苯基四羧酸二酐、三菱化學股份有限公司製、分子量294.22)5.068g(0.017莫耳)、作為溶劑之N-甲基-2-吡咯烷酮74.14g、作為觸媒之吡啶0.68g以及作為脫水劑之甲苯23.70g，將反應器內升溫至180℃為止。一邊使用迪安-斯塔克裝置除去由於醯亞胺化反應而產生之水，一邊在180℃進行3小時之加熱閉環反應之後，復在相同溫度下進行加熱2小時而除去吡啶及甲苯。反應結束後，將冷卻至80℃以下之反應液使用孔徑3μm之鐵氟隆(註冊商標)製之過濾器施行加壓過濾，藉此而得到含有14質量%聚醯亞胺之底覆層樹脂清漆(在以下，成為B-3。)150g。底覆層樹脂之數平均分子量係33,000，重量平均分子量係143,800。由原料之加入量而算出之理論羥基當量係1500g/eq.。 In a 500 ml reactor equipped with a thermometer, a reflux cooler, a Dean-Stark device, a powder introduction port, a nitrogen introduction device, and a stirring device, APB-N (1,3-bis-(3-aminophenoxy)benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) as a diamine compound, 1.08 g (0.003 mol), m-TBHG (4) , 4'-Diamino-2,2'-dimethylbiphenyl, and Gosan Seika Chemical Co., Ltd., molecular weight 212.29) 7.04g (0.033 mol), HAB (3,3'-diamino group -4,4'-dihydroxybiphenyl, manufactured by Nippon Kayaku Co., Ltd., molecular weight 216.24), 1.53 g (0.007 mol), and 54.68 g of N-methyl-2-pyrrolidone as a solvent, while flowing dry nitrogen Stir at 70 ° C for 30 minutes. Then, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22), 8.02 g (0.026 mol), BPDA (3, 3', 4, as a tetracarboxylic dianhydride) was added. 4'-biphenyltetracarboxylic dianhydride, manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22) 5.068 g (0.017 mol), N-methyl-2-pyrrolidone 74.14 g as a solvent, pyridine 0.68 as a catalyst g and 23.70 g of toluene as a dehydrating agent, and the temperature in the reactor was raised to 180 °C. While removing water due to the hydrazine imidization reaction using a Dean-Stark apparatus, heating and ring closure reaction was carried out at 180 ° C for 3 hours, and then heating was carried out at the same temperature for 2 hours to remove pyridine and toluene. After the completion of the reaction, the reaction liquid cooled to 80 ° C or lower was subjected to pressure filtration using a filter made of Teflon (registered trademark) having a pore size of 3 μm, thereby obtaining a bottom coating resin containing 14% by mass of polyimine. Varnish (below B-3.) 150g. The undercoat resin had a number average molecular weight of 33,000 and a weight average molecular weight of 143,800. The theoretical hydroxyl equivalent calculated from the amount of the raw material added was 1500 g/eq.

合成例4 Synthesis Example 4

在附有溫度計、迴流冷卻器、迪安-斯塔克裝置、粉體 導入口、氮導入裝置及攪拌裝置之500ml之反應器中，加入作為二胺化合物之APB-N(1,3-雙-(3-胺基苯氧基)苯、三井化學股份有限公司製、分子量292.33)5.14g(0.018莫耳)、MODABAN(4,4’-二胺基-2’-甲氧基苯甲醯苯胺、日本純良藥品股份有限公司製、分子量257.29)4.52g(0.018莫耳)、HAB(3,3’-二胺基-4,4’-二羥基聯苯、日本化藥股份有限公司製、分子量216.24)1.64g(0.008莫耳)以及作為溶劑之N-甲基-2-吡咯烷酮45.20g，一邊流動乾燥氮一邊在70℃攪拌30分鐘。然後添加作為四羧酸二酐之ODPA(4,4’-氧基二苯二甲酸酐、Manac股份有限公司製、分子量310.22)13.00g(0.042莫耳)、作為溶劑之N-甲基-2-吡咯烷酮52.00g、作為觸媒之吡啶0.66g以及作為脫水劑之甲苯21.00g，將反應器內升溫至180℃。一邊使用迪安-斯塔克裝置除去由於醯亞胺化反應而產生之水一邊在180℃進行3小時之加熱閉環反應之後，赴在相同溫度進行加熱2小時而除去吡啶及甲苯。反應結束後，將冷卻至80℃以下之反應液使用孔徑3μm之鐵氟隆(註冊商標)製之過濾器施行加壓過濾，藉此而得到含有14質量%聚醯亞胺之底覆層樹脂清漆(以下為B-4。)120g。底覆層樹脂之數平均分子量係12,900，重量平均分子量係83,900。由原料之加入量而算出之理論羥基當量係1500g/eq.。 With thermometer, reflux cooler, Dean-Stark device, powder APB-N (1,3-bis-(3-aminophenoxy)benzene, which is a diamine compound, is manufactured by Mitsui Chemicals Co., Ltd., in a 500 ml reactor of the inlet, the nitrogen inlet, and the stirring device. Molecular weight: 292.33) 5.14g (0.018 mol), MODABAN (4,4'-diamino-2'-methoxybenzamide, manufactured by Nippon Pure Pharmaceutical Co., Ltd., molecular weight 257.29) 4.52g (0.018 mol) ), HAB (3,3'-diamino-4,4'-dihydroxybiphenyl, manufactured by Nippon Kayaku Co., Ltd., molecular weight 216.24) 1.64 g (0.008 mol) and N-methyl as solvent 45.20 g of 2-pyrrolidone was stirred at 70 ° C for 30 minutes while flowing dry nitrogen. Then, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22), 13.00 g (0.042 mol) as a tetracarboxylic dianhydride, and N-methyl-2 as a solvent were added. 52.00 g of pyrrolidone, 0.66 g of pyridine as a catalyst, and 21.00 g of toluene as a dehydrating agent, the temperature in the reactor was raised to 180 °C. While removing the water generated by the hydrazine imidization reaction using a Dean-Stark apparatus, the mixture was heated at a temperature of 180 ° C for 3 hours, and then heated at the same temperature for 2 hours to remove pyridine and toluene. After the completion of the reaction, the reaction liquid cooled to 80 ° C or lower was subjected to pressure filtration using a filter made of Teflon (registered trademark) having a pore size of 3 μm, thereby obtaining a bottom coating resin containing 14% by mass of polyimine. Varnish (hereinafter B-4.) 120g. The undercoat resin had a number average molecular weight of 12,900 and a weight average molecular weight of 83,900. The theoretical hydroxyl equivalent calculated from the amount of the raw material added was 1500 g/eq.

合成例5 Synthesis Example 5

在附有溫度計、迴流冷卻器、迪安-斯塔克裝置、粉體導入口、氮導入裝置及攪拌裝置之500ml之反應器中，加 入作為二胺化合物之APB-N(1,3-雙-(3-胺基苯氧基)苯、三井化學股份有限公司製、分子量292.33)0.87g(0.003莫耳)、TFMB(2,2’-雙(三氟甲基)-4,4’-二胺基聯苯、東麗精細化工股份有限公司製、分子量320.23)8.57g(0.027莫耳)、HAB(3,3’-二胺基-4,4’-二羥基聯苯、日本化藥股份有限公司製、分子量216.24)1.48g(0.007莫耳)以及作為溶劑之N-甲基-2-吡咯烷酮80.07g，一邊流動乾燥氮一邊在70℃攪拌30分鐘。然後添加作為四羧酸二酐之ODPA(4,4’-氧基二苯二甲酸酐、Manac股份有限公司製、分子量310.22)5.56g(0.018莫耳)、BPDA(3,3’,4,4’-聯苯基四羧酸二酐、三菱化學股份有限公司製、分子量294.22)5.27g(0.018莫耳)、作為溶劑之N-甲基-2-吡咯烷酮79.46g、作為觸媒之吡啶0.57g以及作為脫水劑之甲苯26.37g，將反應器內升溫至180℃。一邊使用迪安-斯塔克裝置除去由於醯亞胺化反應而產生之水一邊在180℃進行3小時之加熱閉環反應之後，復在相同溫度進行加熱2小時而除去吡啶及甲苯。在反應結束後，將冷卻至80℃以下之反應液使用孔徑3μm之鐵氟隆(註冊商標)製之過濾器施行加壓過濾，藉此而得到含有12質量%聚醯亞胺之底覆層樹脂清漆(以下為B-5。)180g。底覆層樹脂之數平均分子量係19,600，重量平均分子量係64,700。由原料之加入量而算出之理論羥基當量係1500g/eq.。 In a 500 ml reactor equipped with a thermometer, a reflux cooler, a Dean-Stark device, a powder introduction port, a nitrogen introduction device, and a stirring device, APB-N (1,3-bis-(3-aminophenoxy)benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33), 0.87 g (0.003 mol), TFMB (2, 2) '-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, manufactured by Toray Fine Chemicals Co., Ltd., molecular weight 320.23) 8.57g (0.027 mol), HAB (3,3'-diamine Base-4,4'-dihydroxybiphenyl, manufactured by Nippon Kayaku Co., Ltd., molecular weight 216.24) 1.48 g (0.007 mol) and N-methyl-2-pyrrolidone 80.07 g as a solvent, while flowing dry nitrogen Stir at 70 ° C for 30 minutes. Then, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22), 5.56 g (0.018 mol), BPDA (3, 3', 4, tetracarboxylic acid dianhydride) was added. 4'-biphenyltetracarboxylic dianhydride, manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22) 5.27 g (0.018 mol), N-methyl-2-pyrrolidone 79.46 g as a solvent, pyridine 0.57 as a catalyst g and 26.37 g of toluene as a dehydrating agent, the temperature in the reactor was raised to 180 °C. While removing the water generated by the hydrazine imidization reaction using a Dean-Stark apparatus, the mixture was heated at a temperature of 180 ° C for 3 hours, and then heated at the same temperature for 2 hours to remove pyridine and toluene. After the completion of the reaction, the reaction liquid cooled to 80 ° C or lower was subjected to pressure filtration using a filter of Teflon (registered trademark) having a pore size of 3 μm, thereby obtaining a primer layer containing 12% by mass of polyimine. Resin varnish (hereinafter B-5.) 180 g. The undercoat resin had a number average molecular weight of 19,600 and a weight average molecular weight of 64,700. The theoretical hydroxyl equivalent calculated from the amount of the raw material added was 1500 g/eq.

合成例6 Synthesis Example 6

在附有溫度計、迴流冷卻器、迪安-斯塔克裝置、粉體 導入口、氮導入裝置及攪拌裝置之500ml之反應器中，加入作為二胺化合物之4-APB(1,3-雙-(4-胺基苯氧基)苯、日本純良藥品股份有限公司製、分子量292.33)1.17g(0.004莫耳)、TSN(3,7-二胺基-2,8-二甲基二苯并噻吩5,5’-二氧化物、和哥山精化股份有限公司製、分子量274.34)9.84g(0.036莫耳)、HAB(3,3’-二胺基-4,4’-二羥基聯苯基、日本化藥股份有限公司製、分子量216.24)1.84g(0.009莫耳)以及作為溶劑之N-甲基-2-吡咯烷酮72.81g，一邊流動乾燥氮一邊在70℃攪拌30分鐘。然後添加作為四羧酸二酐之ODPA(4,4’-氧基二苯二甲酸酐、Manac股份有限公司製、分子量310.22)8.83g(0.028莫耳)、BPDA(3,3’,4,4’-聯苯基四羧酸二酐、三菱化學股份有限公司製、分子量294.22)5.58g(0.019莫耳)、作為溶劑之N-甲基-2-吡咯烷酮81.65g、作為觸媒之吡啶0.75g以及作為脫水劑之甲苯26.42g，將反應器內升溫至180℃。一邊使用迪安-斯塔克裝置除去由於醯亞胺化反應而產生之水一邊在180℃進行3小時之加熱閉環反應之後，復在相同溫度進行加熱2小時而除去吡啶及甲苯。在反應結束後，將冷卻至80℃以下之反應液使用孔徑3μm之鐵氟隆(註冊商標)製之過濾器施行加壓過濾，藉此而得到含有15質量%聚醯亞胺之底覆層樹脂清漆(以下為B-6。)180g。底覆層樹脂之數平均分子量係19,600，重量平均分子量係85,700。由原料之加入量而算出之理論羥基當量係1500g/eq.。 With thermometer, reflux cooler, Dean-Stark device, powder 4-APB (1,3-bis-(4-aminophenoxy)benzene), which is a diamine compound, was added to a 500 ml reactor of a inlet, a nitrogen introduction device, and a stirring device, and manufactured by Nippon Pure Pharmaceutical Co., Ltd. , molecular weight 292.33) 1.17g (0.004 moles), TSN (3,7-diamino-2,8-dimethyldibenzothiophene 5,5'-dioxide, and Gosan Refinery Co., Ltd. System, molecular weight 274.34) 9.84g (0.036 mol), HAB (3,3'-diamino-4,4'-dihydroxybiphenyl, manufactured by Nippon Kayaku Co., Ltd., molecular weight 216.24) 1.84g (0.009 Moor and 72.81 g of N-methyl-2-pyrrolidone as a solvent were stirred at 70 ° C for 30 minutes while flowing dry nitrogen. Then, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22), 8.83 g (0.028 mol), BPDA (3, 3', 4, as a tetracarboxylic dianhydride) was added. 4'-biphenyltetracarboxylic dianhydride, manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22) 5.58 g (0.019 mol), N-methyl-2-pyrrolidone 81.65 g as a solvent, and pyridine 0.75 as a catalyst g and 26.42 g of toluene as a dehydrating agent, and the temperature in the reactor was raised to 180 °C. While removing the water generated by the hydrazine imidization reaction using a Dean-Stark apparatus, the mixture was heated at a temperature of 180 ° C for 3 hours, and then heated at the same temperature for 2 hours to remove pyridine and toluene. After the completion of the reaction, the reaction liquid cooled to 80 ° C or lower was subjected to pressure filtration using a filter of Teflon (registered trademark) having a pore size of 3 μm, thereby obtaining a primer layer containing 15% by mass of polyimine. Resin varnish (hereinafter B-6.) 180 g. The undercoat resin had a number average molecular weight of 19,600 and a weight average molecular weight of 85,700. The theoretical hydroxyl equivalent calculated from the amount of the raw material added was 1500 g/eq.

(i)合成例1至6得到之聚醯亞胺之物性評價 (i) Evaluation of physical properties of the polyimine obtained in Synthesis Examples 1 to 6

使用自動塗佈機(安田精機製作所股份有限公司製)將合成例1至6得到之各樹脂清漆(B-1)至(B-6)塗佈在PET薄膜上而使乾燥後之膜厚為20μm，在130℃乾燥塗膜30分鐘。然後，將由PET薄膜剝離而得之樹脂膜於SUS製之模框以醯亞胺帶(tape)固定並在200℃進行1小時之追加乾燥而完全除去殘留溶劑，藉此得到單為聚醯亞胺之薄膜。就得到之薄膜而言，使用PerkinElmer公司製之TMA7(Thermomechanical Analyzer(熱機械分析儀))，一邊以200mN之加重拉張切割成為4mm幅寬之薄膜，一邊由50℃開始加熱至350℃為止，測定線膨脹係數之轉移溫度(玻璃轉移溫度、Tg)及50至150℃間之線膨脹係數(CTE)。將結果表示在表1及表2。此外，表1中之「無Tg(收縮)」係表示無明確之玻璃轉移溫度並因溫度上升而引起收縮。 Each of the resin varnishes (B-1) to (B-6) obtained in Synthesis Examples 1 to 6 was applied onto a PET film using an automatic coater (manufactured by Yasuda Seiki Co., Ltd.) to make the film thickness after drying The film was dried at 130 ° C for 30 minutes at 20 μm. Then, the resin film obtained by peeling off the PET film was fixed in a frame made of SUS with a ruthenium tape and dried at 200 ° C for 1 hour to completely remove the residual solvent, thereby obtaining a single polysiloxane. A film of amine. In the obtained film, a TMA7 (Thermomechanical Analyzer) manufactured by PerkinElmer Co., Ltd. was used, and the film was cut into a film having a width of 4 mm by a weighting of 200 mN, and heated from 50 ° C to 350 ° C. The transfer temperature (glass transition temperature, Tg) of the linear expansion coefficient and the linear expansion coefficient (CTE) between 50 and 150 ° C were measured. The results are shown in Tables 1 and 2. Further, "no Tg (shrinkage)" in Table 1 means that there is no clear glass transition temperature and shrinkage due to an increase in temperature.

實施例1至6、比較例1至4 Examples 1 to 6 and Comparative Examples 1 to 4

銅箔(A)係使用製作例1得到之銅箔(A-1)，比較銅箔係使用製作例2得到之銅箔(A-2)、BHY(壓延銅箔、日鑛金屬股份有限公司製；以下為(A’-1)。)(無表面粗糙化處理)及CF-T9FZ-HTE(電解銅箔、福田金屬箔粉工業股份有限公司製；以下為(A’-2)。)(無表面粗糙化處理)，底覆層樹脂(B)係使用合成例1至6得到之各樹脂清漆(B-1)至(B-6)。藉由表1及表2所示之組合而在A-1銅箔之被覆層表面上、其他銅箔之無粗糙化處理表面上，除了比較例1以外，以使乾燥後之膜厚為2μm之方式用自動塗佈機(安田精機 製作所股份有限公司製)將各樹脂清漆塗佈在各銅箔上。藉由在130℃乾燥塗膜10分鐘，而得到設置底覆層之銅箔。接著使用作為聚醯亞胺樹脂前驅物(C)之KAYAFLEX KPI-126(日本化藥股份有限公司製；包含兩末端為胺基之聚醯胺酸樹脂和前式(8)之四羧酸衍生物之樹脂清漆)(將該樹脂作為(C-1))，以使醯亞胺化後之膜厚成為25μm之方式，藉由鑄模法塗佈該樹脂清漆，比較例1係直接塗佈在A-1銅箔之被覆層表面，其他係塗佈在前述底覆層上。藉由在130℃乾燥塗膜10分鐘之後，復在350℃進行2小時之醯亞胺化，而得到本發明之覆銅積層板以及比較試驗用之覆銅積層板。 Copper foil (A) was obtained by using the copper foil (A-1) obtained in Production Example 1, and copper foil (A-2) and BHY (rolled copper foil, Nissan Metal Co., Ltd.) obtained in Comparative Example 2 were used as the copper foil. The following are (A'-1).) (no surface roughening treatment) and CF-T9FZ-HTE (electrolytic copper foil, Fukuda Metal Foil Powder Co., Ltd.; the following is (A'-2).) (No surface roughening treatment), the undercoat resin (B) used each of the resin varnishes (B-1) to (B-6) obtained in Synthesis Examples 1 to 6. By the combination shown in Table 1 and Table 2, on the surface of the coating layer of the A-1 copper foil and the surface of the other copper foil without roughening, except for Comparative Example 1, the film thickness after drying was 2 μm. Automatic coating machine (Yaoda Seiki) Each resin varnish was applied to each copper foil. The copper foil provided with the undercoat layer was obtained by drying the coating film at 130 ° C for 10 minutes. Next, KAYAFLEX KPI-126 (manufactured by Nippon Kayaku Co., Ltd.; which is a polyaminophthalic acid resin having an amine group at both ends and a tetracarboxylic acid derivative of the above formula (8), which is a precursor of the polyimine resin (C), is used. (Resin resin varnish) (this resin was used as (C-1)), and the resin varnish was applied by a molding method so that the film thickness after ruthenium formation was 25 μm, and Comparative Example 1 was directly coated on the resin varnish. The surface of the coating layer of the A-1 copper foil is coated on the undercoat layer. The coating of the copper-clad laminate of the present invention and the copper-clad laminate for comparative test were obtained by drying the coating film at 130 ° C for 10 minutes and then performing the imidization at 350 ° C for 2 hours.

(ii)本發明及比較用之覆銅積層板之評價 (ii) Evaluation of the copper-clad laminate of the present invention and comparative use

使用實施例1至6及比較例1至4得到之覆銅積層板進行下列之評價。 The copper-clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to the following evaluations.

(1)銅箔之剝離強度 (1) Peel strength of copper foil

在實施例1至6及比較例1至4得到之覆銅積層板之銅箔側表面貼附遮罩用膠帶(商品名稱：clearlinetape No.557、NICHIBAN股份有限公司製)之後，在加熱至40℃之蝕刻液(氯化鐵水溶液、波美(Baume)比重度為45°)中進行30分鐘之蝕刻，剝離遮罩用膠帶而形成10mm之銅箔圖案。接著使用接著用薄片將聚醯亞胺樹脂層側貼附於補強板，使用刀片由聚醯亞胺剝離10mm幅寬之銅箔端部，使用拉力試驗機(AUTOGRAPH：島津製作所股份有限公司製)測定在90°方向之銅箔和聚醯亞胺樹脂層之間之剝離強度，將 此作為常態剝離強度。此外，常態係表示將得到之覆銅積層板放置於常溫(25℃)之狀態。此外，將在150℃保持該積層板168小時後之剝離強度作為耐熱剝離強度，將在40℃、95% RH保持96小時後之剝離強度作為耐濕熱剝離強度。將結果表示在表1及表2。 After attaching a masking tape (trade name: clearlinetape No. 557, manufactured by NICHIBAN Co., Ltd.) to the copper foil side surface of the copper-clad laminate obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the mixture was heated to 40. The etching solution of °C (iron chloride aqueous solution, Baume specific gravity: 45°) was etched for 30 minutes, and the mask tape was peeled off to form a 10 mm copper foil pattern. Then, the side of the polyimide film layer was attached to the reinforcing sheet by using a sheet, and the end of the copper foil having a width of 10 mm was peeled off from the polyimide by using a blade, and a tensile tester (AUTOGRAPH: manufactured by Shimadzu Corporation) was used. Determining the peel strength between the copper foil and the polyimide layer in the 90° direction, This is the normal peel strength. Further, the normal state indicates that the obtained copper clad laminate is placed at a normal temperature (25 ° C). Further, the peel strength after holding the laminate for 168 hours at 150 ° C was taken as the heat-resistant peel strength, and the peel strength after holding at 40 ° C and 95% RH for 96 hours was taken as the moisture-resistant peel strength. The results are shown in Tables 1 and 2.

(2)起泡之確認 (2) Confirmation of blistering

藉由目視而觀察實施例1至6及比較例1至4得到之覆銅積層板之外觀，藉由下列之基準而進行評價。將結果表示在表1及表2。 The appearance of the copper clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was visually observed, and evaluated by the following criteria. The results are shown in Tables 1 and 2.

○：無起泡、無外觀上之問題 ○: no blistering, no appearance problems

△：僅看見些微(一部分)之起泡 △: Only a slight (partial) blistering is seen

×：有起泡、有外觀上之問題 ×: There is foaming and appearance problems.

(3)防銹效果之確認 (3) Confirmation of rust prevention effect

藉由目視而觀察實施例1至6及比較例1至4得到之覆銅積層板之外觀，藉由下列之基準而進行評價。將結果表示在表1及表2。 The appearance of the copper clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was visually observed, and evaluated by the following criteria. The results are shown in Tables 1 and 2.

○：藉由目視而無看見銅箔之氧化 ○: No visible copper oxide oxidation by visual inspection

×：藉由目視而確認由於銅箔氧化造成之變色 ×: Confirmation of discoloration due to oxidation of copper foil by visual observation

(4)耐熱性試驗 (4) Heat resistance test

將實施例1至6及比較例1至4得到之覆銅積層板漂浮於260℃之焊接浴，藉由目視而觀察外觀，藉由下列之基準而進行評價。將結果表示在表1及表2。 The copper-clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were floated in a welding bath at 260 ° C, and the appearance was observed by visual observation, and evaluated by the following criteria. The results are shown in Tables 1 and 2.

○：無外觀之變化 ○: no change in appearance

×：看見膨脹、變色等之外觀異常 ×: The appearance of swelling, discoloration, etc. is abnormal.

(5)捲曲之確認 (5) Confirmation of curl

將實施例1至6及比較例1至4得到之覆銅積層板切取為5cm正方形(5cm square)(一邊為5cm之正方形)，並測定曲率半徑。此外，使用前述之蝕刻液而對於各覆銅積層板之銅箔側進行全面蝕刻，並同樣地測定曲率半徑。將結果表示在表1及表2。 The copper clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were cut into 5 cm squares (squares of 5 cm on one side), and the radius of curvature was measured. Further, the copper foil side of each of the copper clad laminates was completely etched using the etching liquid described above, and the radius of curvature was measured in the same manner. The results are shown in Tables 1 and 2.

若與無底覆層之比較例1相比，本發明之使用銅箔(A-1)及底覆層樹脂(B-1)之實施例1之覆銅積層板在常態、耐熱及耐濕熱任一情形下剝離強度明顯較高，且即使 是在防銹效果之方面也較優異。此外，若比較使用無具有Ni、Cr被覆層之銅箔之比較例2及3、和本發明實施例2，本發明在常態、耐熱及耐濕熱之任一情形下剝離強度明顯較高，且即使是在耐熱性之方面也明顯較優異。此外，比起藉由電鍍法而在設置Ni、Cr被覆層之銅箔(A-2)上設置與實施例2相同之底覆層樹脂(B)層之比較例4，使用銅箔(A-1)之實施例2之覆銅積層板在常態、耐熱及耐濕熱之任一種情形下剝離強度顯示呈顯著地高之值。此外，比起比較例之任一種，本發明之實施例3至6在常態、耐熱及耐濕熱之任一種情形下剝離強度顯示呈顯著地高之值，比起比較例2至4，本發明之實施例3至6即使是在蝕刻後之曲率半徑及底覆樹脂之線膨脹係數也表示良好值。由此可明顯得知：銅箔(A-1)具有藉由濺鍍法而設置之極薄且厚度均一之Ni、Cr被覆層，在銅箔(A-1)其被覆層表面，透過由特定溶媒可溶性聚醯亞胺而組成之底覆樹脂層(B)而接著聚醯亞胺層(D)之本發明之覆銅積層板，皆在常態、耐熱及耐濕熱之任一種情形下剝離強度顯著地高，耐熱性也高，且具有防銹效果，在實施例2至6中也無起泡，且在實施例3至6中即使是蝕刻後之曲率半徑也顯著地良好，作為覆銅積層板是極為有用地。 The copper clad laminate of the first embodiment using the copper foil (A-1) and the undercoat resin (B-1) of the present invention is in a normal state, heat resistance and moist heat resistance as compared with Comparative Example 1 without a bottom coating. Peel strength is significantly higher in either case, and even It is also excellent in terms of anti-rust effect. Further, when Comparative Examples 2 and 3 having no copper foil having a Ni and Cr coating layer were used in comparison, and Example 2 of the present invention, the peel strength of the present invention was significantly higher in any of normal, heat and humidity resistance, and Even in terms of heat resistance, it is significantly superior. In addition, Comparative Example 4 in which the undercoat resin (B) layer similar to that of Example 2 was provided on the copper foil (A-2) provided with the Ni and Cr coating layers by the plating method was used, and copper foil (A) was used. -1) The copper-clad laminate of Example 2 showed a markedly high peel strength in either of the normal state, heat resistance and heat and humidity resistance. Further, the peeling strengths of Examples 3 to 6 of the present invention showed a significantly higher value in any of the normal state, heat resistance and moist heat resistance than any of the comparative examples, and the present invention was compared with Comparative Examples 2 to 4. Examples 3 to 6 showed good values even if the radius of curvature after etching and the coefficient of linear expansion of the undercoat resin. From this, it is apparent that the copper foil (A-1) has an extremely thin and uniform thickness Ni and Cr coating layer provided by sputtering, and the copper foil (A-1) is coated on the surface of the coating layer. The copper-clad laminate of the present invention comprising the base resin layer (B) composed of a specific solvent-soluble polyimide and then the polyimide layer (D) is stripped in any of normal, heat-resistant and moist heat-resistant conditions. The strength is remarkably high, the heat resistance is also high, and the rust preventing effect is obtained. In Examples 2 to 6, there is no blistering, and in Examples 3 to 6, even the radius of curvature after etching is remarkably good as a coating. Copper laminates are extremely useful.

[產業上之可利用性] [Industrial availability]

本發明之覆銅積層板在常態、耐熱及耐濕熱之任一種情形之剝離強度皆顯著地高，焊接耐熱性等之耐熱性也高，且具有防銹效果，並且可以藉由選擇底覆樹脂(B)之組 成而消除形成聚醯亞胺樹脂層時(對於聚醯亞胺樹脂前驅物(C)層進行醯亞胺化時)之起泡，加大在蝕刻後之曲率半徑(縮小在蝕刻後之彎曲)。因此，在電機電子材料領域極為有用。 The copper clad laminate of the present invention has remarkably high peel strength in any of normal state, heat resistance and moist heat resistance, high heat resistance such as solder heat resistance, and rust preventive effect, and can be selected by selecting a base resin. Group (B) To eliminate the foaming when forming the polyimide layer (when the polyimide layer of the polyimide (C) layer is imidized), increase the radius of curvature after etching (reducing the curvature after etching) ). Therefore, it is extremely useful in the field of electrical and electronic materials.

Claims (9)

一種覆銅積層板，其係在無施行粗糙化處理之銅箔(A)上設置之被覆層表面，具有包含溶媒可溶性聚醯亞胺之底覆層(primer)樹脂(B)層，並且在其上具有直接接著之聚醯亞胺層(D)，而且滿足下列(1)至(4)要件之覆銅積層板，(1)該被覆層係藉由自銅箔表面依序積層之Ni層及Cr層而構成、(2)該被覆層之Ni及Cr被覆量分別為15至440μg/dm2及15至210μg/dm2、(3)該被覆層之厚度最大值係0.5至5nm，且最小值為最大值之80%以上、(4)溶媒可溶性聚醯亞胺係藉由使下列(i)或(ii)所述之芳香族四元酸二酐與下列(iii)或(iv)所述之芳香族二胺反應而得到之數平均分子量為1,000至50,000且重量平均分子量為5,000至500,000之閉環型聚醯亞胺樹脂；(i)下式(1)所示之氧基二苯二甲酸二酐 (ii)該氧基二苯二甲酸二酐與其他芳香族四元酸二酐之至少1種的兩種者； (iii)下式(2)所示之雙(胺基苯氧基)苯 (iv)該雙(胺基苯氧基)苯與其他芳香族二胺之至少1種的兩種者。 A copper clad laminate which is provided on a surface of a coating layer provided on a copper foil (A) which is not subjected to roughening treatment, and has a primer resin (B) layer containing a solvent-soluble polyimine, and a copper-clad laminate having a layer of polyimine directly adjacent thereto (D) and satisfying the following requirements (1) to (4), (1) the coating layer is sequentially laminated with Ni from the surface of the copper foil The layer and the Cr layer are formed, (2) the coating layer has a Ni and Cr coating amount of 15 to 440 μg/dm 2 and 15 to 210 μg/dm 2 , respectively, and (3) the coating layer has a maximum thickness of 0.5 to 5 nm. And the minimum value is 80% or more of the maximum value, and (4) the solvent-soluble polyimine is obtained by the following (i) or (ii) of the aromatic tetrabasic dianhydride and the following (iii) or (iv) a closed-loop polyimine resin having a number average molecular weight of 1,000 to 50,000 and a weight average molecular weight of 5,000 to 500,000 obtained by the reaction of the aromatic diamine; (i) an oxy group represented by the following formula (1) Phthalic anhydride (ii) at least one of the oxydiphthalic dianhydride and another aromatic tetrabasic acid dianhydride; (iii) bis(aminophenoxy)benzene represented by the following formula (2) (iv) at least one of the bis(aminophenoxy)benzene and the other aromatic diamine. 如申請專利範圍第1項所述之覆銅積層板，其中，式(2)以外之芳香族二胺之至少1種係由3,3’-二胺基-4,4’-二羥基二苯基醚、3,3’-二胺基-4,4’-二羥基二苯基碸、3,3’-二胺基-4,4’-二羥基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、2,2-雙(3-胺基-4-羥基苯基)丙烷、1,3-六氟-2,2-雙(3-胺基-4-羥基苯基)丙烷、1,3-雙(4-胺基-3-羥基苯氧基)苯及9,9’-雙(3-胺基-4-羥基苯基)芴所組成群組選出之至少1種二胺基二酚(diaminodiphenol)類。 The copper-clad laminate according to claim 1, wherein at least one of the aromatic diamines other than the formula (2) is composed of 3,3'-diamino-4,4'-dihydroxy Phenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-di Hydroxy-4,4'-diaminobiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino- a group consisting of 4-hydroxyphenyl)propane, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene and 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene At least one diaminodiphenol selected from the group. 如申請專利範圍第1項所述之覆銅積層板，其中，使用於前述反應之四元酸二酐為(i)或(ii)或(iii)，(i)式(1)之氧基二苯二甲酸二酐單獨者；(ii)式(1)之氧基二苯二甲酸二酐，與由下式(3)所示之聯苯四羧酸二酐及均苯四甲酸酐所組成群組選出之至少1種芳香族四元酸二酐兩種併用者； (iii)在前述(i)或(ii)中，復加入其他芳香族四元酸二酐之至少1種之兩者併用或三種併用者；使用於前述反應之二胺係(i)或(ii)者，(i)式(2)之雙(胺基苯氧基)苯與由下式(4)所述之芳香族二胺所組成群組選出之至少1種兩種併用者； (式(4)中，R4係表示甲基，R5係表示氫原子、甲基、乙基、甲氧基或三氟甲基)；或(ii)在前述(i)中，復加入前述(i)以外之芳香族二胺之至少1種之三種併用者。 The copper-clad laminate according to claim 1, wherein the tetrabasic acid dianhydride used in the above reaction is (i) or (ii) or (iii), (i) an oxy group of the formula (1) a dicarboxylic acid dianhydride alone; (ii) an oxydiphthalic dianhydride of the formula (1), and a biphenyltetracarboxylic dianhydride and a pyromellitic anhydride represented by the following formula (3) Combining at least one aromatic tetrabasic acid dianhydride selected from the group; (iii) in the above (i) or (ii), a combination of at least one of the other aromatic tetrabasic acid dianhydrides or a combination of three; the diamine system (i) or (for the aforementioned reaction) Ii), (i) at least one of the bis(aminophenoxy)benzene of the formula (2) and at least one selected from the group consisting of the aromatic diamines of the following formula (4); (In the formula (4), R 4 represents a methyl group, R 5 represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group or a trifluoromethyl group); or (ii) in the above (i), a complex addition At least one of the three types of aromatic diamines other than the above (i) is used in combination. 如申請專利範圍第1至3項中任一項所述之覆銅積層板，其中，在無施行粗糙化處理之銅箔(A)上設置之被覆層係藉由濺鍍法而形成。 The copper clad laminate according to any one of claims 1 to 3, wherein the coating layer provided on the copper foil (A) which is not subjected to the roughening treatment is formed by a sputtering method. 如申請專利範圍第1至4項中任一項所述之覆銅積層板，其中，直接接著於底覆層樹脂(B)層之聚醯亞胺層 (D)，其係將包含對應之聚醯胺酸之聚醯亞胺樹脂前驅物(C)層藉由加熱進行醯亞胺化而得之聚醯亞胺層(D)。 The copper-clad laminate according to any one of claims 1 to 4, wherein the polyimide layer directly adjacent to the undercoat resin (B) layer (D), which is a polyimine layer (D) obtained by subjecting a polyimine resin precursor precursor (C) layer of a corresponding polyphthalic acid to ruthenium iodization by heating. 如申請專利範圍第1至5項中任一項所述之覆銅積層板，其中，底覆層樹脂(B)層係將包含底覆層樹脂(B)之樹脂清漆塗佈在設置於銅箔(A)上之被覆層表面並乾燥而得者，且該底覆層樹脂(B)層之厚度係0.5至20μm。 The copper clad laminate according to any one of claims 1 to 5, wherein the undercoat resin (B) layer coats the resin varnish containing the undercoat resin (B) on the copper. The surface of the coating layer on the foil (A) is dried and obtained, and the thickness of the undercoat resin (B) layer is 0.5 to 20 μm. 如申請專利範圍第6項所述之覆銅積層板，其中，包含底覆層樹脂(B)之樹脂清漆係將溶媒可溶性聚醯亞胺溶解於由N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基甲醯胺、γ-丁內酯、環戊酮及安息香酸甲酯所組成群組選出之至少1種溶媒之樹脂清漆。 The copper-clad laminate according to claim 6, wherein the resin varnish comprising the undercoat resin (B) dissolves the solvent-soluble polyimine in N-methyl-2-pyrrolidone, N, At least 1 selected from the group consisting of N-dimethylacetamide, N,N-dimethylformamide, N-methylformamide, γ-butyrolactone, cyclopentanone, and methyl benzoate A solvent resin varnish. 如申請專利範圍第5至7項中任一項所述之覆銅積層板，其中，包含聚醯胺酸之聚醯亞胺樹脂前驅物(C)層係含有下式(7)所示之末端具有胺基之聚醯胺酸、以及下式(8)所示之四羧酸衍生物， (式(7)中，R6係表示4價之芳香族基，R7係表示2價之芳香族基，x係平均重複數而表示1以上之實數) (式(8)中，R8係表示4價之芳香族基，R9係表示氫原子或C1至C3烷基)。 The copper-clad laminate according to any one of claims 5 to 7, wherein the polyamidene resin precursor (C) layer comprising poly-proline contains the formula (7) a polyamic acid having an amine group at the terminal, and a tetracarboxylic acid derivative represented by the following formula (8), (In the formula (7), R 6 represents a tetravalent aromatic group, R 7 represents a divalent aromatic group, and x is an average repeat number and represents a real number of 1 or more) (In the formula (8), R 8 represents a tetravalent aromatic group, and R 9 represents a hydrogen atom or a C1 to C3 alkyl group). 一種配線基板，其係使用申請專利範圍第1至8項中任一項所述之覆銅積層板者。 A wiring board using the copper-clad laminate according to any one of claims 1 to 8.
TW101111334A 2012-03-30 2012-03-30 Copper-clad laminated plate having primer layer, and wiring board using the laminated plate TW201338970A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW101111334A TW201338970A (en) 2012-03-30 2012-03-30 Copper-clad laminated plate having primer layer, and wiring board using the laminated plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW101111334A TW201338970A (en) 2012-03-30 2012-03-30 Copper-clad laminated plate having primer layer, and wiring board using the laminated plate

Publications (1)

Publication Number Publication Date
TW201338970A true TW201338970A (en) 2013-10-01

Family

ID=49770694

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101111334A TW201338970A (en) 2012-03-30 2012-03-30 Copper-clad laminated plate having primer layer, and wiring board using the laminated plate

Country Status (1)

Country Link
TW (1) TW201338970A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI573816B (en) * 2016-05-11 2017-03-11 台虹科技股份有限公司 Polyimide precursor composition and application thereof
US11782344B2 (en) 2015-04-21 2023-10-10 Fujifilm Electronic Materials U.S.A., Inc. Photosensitive polyimide compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11782344B2 (en) 2015-04-21 2023-10-10 Fujifilm Electronic Materials U.S.A., Inc. Photosensitive polyimide compositions
US11899364B2 (en) 2015-04-21 2024-02-13 Fujifilm Electronic Materials U.S.A., Inc. Photosensitive polyimide compositions
TWI573816B (en) * 2016-05-11 2017-03-11 台虹科技股份有限公司 Polyimide precursor composition and application thereof

Similar Documents

Publication Publication Date Title
JP7469383B2 (en) Metal-clad laminates and circuit boards
TWI398548B (en) Solution, plating material, insulating sheet, laminate, and printed wiring board
TWI721133B (en) Polyamide acid, thermoplastic polyimide, resin film, metal-clad laminate and circuit board
JP5469578B2 (en) Copper-clad laminate having primer layer and wiring board using the same
TW201544528A (en) Polyimide laminate and manufacturing process thereof
JPWO2007148666A1 (en) Copper foil with primer resin layer and laminate using the same
JP2008265069A (en) Insulating adhesion sheet, laminate, and printed wiring board
TW201525068A (en) Polyamic acid composition, polyimide, resin film, and metal clad laminate
KR20100016403A (en) Copper foil with resin layer
TW202337693A (en) Multilayer circuit board and method of manufacturing the same
TW201609867A (en) Multilayer polyimide film, method of producing multilayer polyimide film, polyimide laminate using same, and copolymer polyimide used therein
JP5345116B2 (en) Copper-clad laminate, manufacturing method thereof, and wiring board including the copper-clad laminate
TWI413460B (en) Laminate for wiring board
TWI431152B (en) Plating material, polyamic acid solution and polyimide resin solution used for the material, and printed wiring board using the material and the solutions
TW201338970A (en) Copper-clad laminated plate having primer layer, and wiring board using the laminated plate
TWI753196B (en) Metal-clad laminate, adhesive sheet, adhesive polyimide resin composition and circuit substrate
WO2013144992A1 (en) Copper-clad laminate having primer layer and wiring board using same
TW201635868A (en) Copper-clad laminated board and printed circuit board
KR102003880B1 (en) Flexible cupper laminated film and Preparing method of the same
TWI683836B (en) Polyimide laminated film, method for producing polyimide laminated film, method for producing thermoplastic polyimide, and method for producing flexible metal clad laminate
TW202319444A (en) Polyamide acid, polyimide, polyimide film, metal-clad laminate and circuit
KR20140073718A (en) Flexible cupper laminated film and Preparing method of the same
WO2013144991A1 (en) Copper-clad laminate, method for producing same, and wiring board comprising copper-clad laminate
TWI654076B (en) Method of forming conductor layer, and method of producing multilayer wiring board using same
JP2009184131A (en) Multilayer laminate and method for producing flexible copper-clad laminate